KR102558721B1 - Composition for solid-state imaging device, infrared shielding film, and solid-state imaging device - Google Patents

Abstract

[Problem] To provide a composition for a solid-state imaging device capable of forming an optical filter for a solid-state imaging device having both good visible light transmittance and infrared ray shielding even when the number of organic dyes contained is small.
[Solution] The present invention is a composition for solid-state imaging devices containing a phthalocyanine compound represented by the following formula (1). In Formula (1), a plurality of R's are each independently an alkyl group or an aryl group. A plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. A plurality of n's 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.

BACKGROUND OF THE INVENTION [0002] A video camera, a digital camera, a mobile phone having a camera function, and the like are equipped with a solid-state imaging device such as a CCD (Charge-Coupled Device) image sensor or a CMOS (Complementary MOS) image sensor. The sensitivity of the photodiode provided in these solid-state imaging devices ranges from the visible light region to the infrared region. For this reason, in the solid-state imaging element, a filter for blocking infrared rays is provided. With this infrared cut-off filter, the sensitivity of the solid-state imaging device can be corrected to be close to human visibility.

The infrared cut filter contains a dye or pigment as an infrared ray shielding agent. The infrared ray shielding agent is required to have a property of absorbing infrared rays while sufficiently transmitting visible light. As one of these infrared shielding agents, in particular, as a good near-infrared shielding agent, using a phthalocyanine compound has been studied (see Japanese Patent Laid-Open No. 2008-201952).

However, even in conventional infrared cut filters using phthalocyanine compounds, visible light transmittance and infrared ray shielding properties are not sufficiently satisfied. Therefore, in order to exhibit the favorable said characteristics, for example, a mixture of multiple types of infrared ray shielding agents may be used. The use of such a large number of types of infrared shielding agents is also a factor that causes reduction in productivity such as high cost. Moreover, in the conventional infrared cutoff filter using a phthalocyanine compound, the fluctuation|variation of the transmittance|permeability may be large in the visible region. Even in this case, good visibility correction is not performed.

Japanese Unexamined Patent Publication No. 2008-201952

However, even in conventional infrared cutoff filters for solid-state imaging devices using phthalocyanine compounds, visible light transmittance and infrared ray shielding properties are not sufficiently satisfied. Therefore, in order to exhibit the favorable said characteristics, for example, a mixture of multiple types of infrared ray shielding agents may be used. The use of such a large number of types of infrared shielding agents is also a factor that causes reduction in productivity such as high cost. Moreover, in the conventional infrared cutoff filter using a phthalocyanine compound, the fluctuation|variation of the transmittance|permeability may be large in the visible region. Even in this case, good visibility correction is not performed.

The present invention has been made based on the above circumstances, and its object is to provide a composition for a solid-state imaging device capable of forming an optical filter for a solid-state imaging device having both good visible light transmittance and infrared shielding properties even when the kind of organic dye contained is small, an infrared shielding film for a solid-state image sensor having both good visible light transmittance and infrared shielding property even when the kind of organic dye contained is small, and a solid-state imaging device having such an infrared shielding film.

The invention made in order to solve the said subject is a composition for solid-state imaging devices containing the phthalocyanine compound (henceforth "[A] phthalocyanine compound") represented by following formula (1).

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

Another invention made in order to solve the said subject is an infrared shielding film (I) formed from the said composition for solid-state imaging devices.

Another invention made to solve the above problems is an infrared shielding film (II) for a solid-state imaging device that substantially contains only one or two organic dyes and satisfies the following (A) to (C).

(A) The average value of the transmittance in the wavelength range of 430 nm or more and 580 nm or less is 75% or more

(B) The average value of the transmittance in the wavelength range of 700 nm or more and 900 nm or less is 16.5% or less

(C) transmittance of 10% or less at a wavelength of 1200 nm

Another invention made to solve the above object is a solid-state imaging device having the infrared shielding film (I) or the infrared shielding film (II).

According to the present invention, it is possible to provide a composition for a solid-state imaging device capable of forming an optical filter for a solid-state imaging device having both good visible light transmittance and infrared shielding properties even when the type of organic dye contained is small, an infrared shielding film for a solid-state imaging device having both good visible light transmittance and infrared shielding property even when the type of organic dye contained is small, and a solid-state imaging device having such an infrared shielding film.

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

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

<Composition for solid-state imaging device>

The composition for solid-state imaging devices according to one embodiment of the present invention (hereinafter, simply referred to as "composition") contains [A] a phthalocyanine compound. The composition preferably further contains [B] an infrared ray shielding agent that is a metal oxide, a copper compound (excluding [A] a phthalocyanine compound) or a combination thereof.

([A] phthalocyanine compound)

[A] A phthalocyanine compound is a compound represented by following formula (1). [A] The phthalocyanine compound has high transmittance in the visible light region (for example, a wavelength range of 430 nm to 580 nm) and high shielding property in the near infrared region (eg, a wavelength range of 700 nm to 900 nm). Since the composition contains such a [A] phthalocyanine compound, an optical filter having both good visible light transmittance and infrared ray shielding properties can be formed even when the number of organic dyes contained is small. In addition, since the composition contains such a [A] phthalocyanine compound, an optical filter having high uniform transmittance in the visible region can be formed.

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

Examples of the alkyl group represented by R include linear or branched alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl and t-butyl.

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

As said R, an alkyl group is preferable, and a C1-C12 linear or branched alkyl group is more preferable. Moreover, as for the upper limit of carbon number of this alkyl group, 6 is preferable, 4 is more preferable, and 2 is still more preferable. As said R, a methyl group is especially preferable.

As a halogen atom represented by said X, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the alkyl group represented by the above X include those exemplified as the alkyl group represented by the above R.

A plurality of X's may be bonded to each other. Usually, among a plurality of X's, two X's bonded to the same benzene ring bond to each other and form an aromatic ring together with the carbon chain to which they are bonded. As an aromatic ring formed, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. The hydrogen atoms of these aromatic rings may be substituted with hydrocarbon groups or other substituents.

As said X, a hydrogen atom is preferable.

Examples of the divalent metal atom represented by M include Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, and Pb. In addition, a divalent metal atom refers to a metal atom that can become a divalent cation.

Here, the derivative of a metal atom refers to an atomic group containing a metal atom. A trivalent metal atom refers to a metal atom capable of becoming a trivalent cation. As a trivalent metal atom, Al, In, etc. are mentioned. A tetravalent metal atom refers to a metal atom capable of becoming a tetravalent cation. As a tetravalent metal atom, Si, Ge, Sn, etc. are mentioned. In addition, a semimetal atom is also contained in a metal atom. Examples of the trivalent or tetravalent metal atom derivative 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 said M, _H2 (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, _SnCl2 , AlCl, VO, and TiO are preferable, and VO is more preferable.

As a lower limit of said n, 4 is preferable. As an upper limit of said n, 5 is preferable and 4 is more preferable.

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

[A] The method for synthesizing the phthalocyanine compound is not particularly limited, and it can be synthesized by combining known methods. For example, it can be synthesized according to scheme 1 below.

In scheme 1, R, X, M and n are synonymous with Expression (1).

In addition, as the dicyano compound in the above scheme 1, a plurality of types of dicyano compounds having different substituents (RO(CH ₂ ) _n - or X) may be used. Examples of sources of metal ions represented ^by M ²⁺ include various metal salts such as acetates, chlorides, bromides, nitrates, and sulfates. The [A] phthalocyanine compound represented by the said formula (1) can be obtained by mixing the compound represented by said formula (0), a metal salt, etc. in a solvent. Examples of the solvent include aromatic hydrocarbons (benzene, toluene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), chlorinated hydrocarbons (methylene chloride, chloroform, dichloroethane, etc.), DMF, DMSO, acetonitrile, THF, N-methylpyrrolidone, dioxane, alcohols (methanol, ethanol, etc.).

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, and still more preferably 1% by mass. On the other hand, as an upper limit of this content, 30 mass % is preferable, 15 mass % is more preferable, 10 mass % is still more preferable, and 5 mass % is still more preferable. [A] By making content of a phthalocyanine compound into the said range, the visible light transmittance and infrared rays shielding property of the optical filter obtained become a more favorable balance.

[A] A phthalocyanine compound may be used individually by 1 type, and may mix and use 2 or more types. However, it is preferable to use only 1 type or 2 types of [A] phthalocyanine compounds, and it is more preferable to use only 1 type of [A] phthalocyanine compounds. [A] A phthalocyanine compound can exhibit good visible light transmittance and infrared shielding property only by one type. Therefore, by reducing the number of types of [A] phthalocyanine compounds to be used, productivity can be increased while exhibiting good visible light transmittance and infrared ray shielding properties.

([B] infrared shielding agent)

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

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

[B] Examples of copper compounds as infrared shielding agents include copper phthalocyanine compounds and other copper complexes. Copper phthalocyanine, chlorinated copper phthalocyanine, chlorinated copper bromide phthalocyanine, brominated copper phthalocyanine, etc. are mentioned as a copper phthalocyanine type compound.

[B] As the infrared shielding agent, a metal oxide is preferable, and a tungsten oxide-based compound is more preferable. A tungsten oxide-based compound is an infrared ray shielding agent that has high absorption of infrared rays (in particular, infrared rays having a wavelength of about 800 nm or more and less than or equal to 1200 nm) (that is, high infrared ray shielding property) and low absorption of visible light. Therefore, when the composition contains a tungsten oxide-based compound, the obtained optical filter can improve its infrared shielding properties while maintaining good visible light transmittance. [B] Infrared shielding agent may be used individually by 1 type, and may mix and use 2 or more types.

As a tungsten oxide type compound, it is more preferable that it is a tungsten oxide type compound represented by following formula (2).

A _x WO _y ... (2)

In 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 alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like. 1 type or 2 or more types may be sufficient as the metal element represented by A.

As said A, an alkali metal is preferable, Rb and Cs are more preferable, and Cs is still more preferable. That is, the metal oxide is more preferably cesium tungsten oxide.

When x in the formula (2) is 0.001 or more, infrared rays can be sufficiently shielded. 0.01 is preferable and, as for the minimum of x, 0.1 is more preferable. On the other hand, when x is 1.1 or less, generation of an impurity phase in the tungsten oxide-based compound can be avoided more reliably. 1 is preferable and, as for the upper limit of x, 0.5 is more preferable.

Chemical stability as a material can be improved more because y in said Formula (2) is 2.2 or more. As for the lower limit of y, 2.5 is preferable. On the other hand, when y is 3.0 or less, infrared rays can be shielded sufficiently.

As a specific example of the tungsten oxide type compound represented by said formula (2), Cs _{0 . 33} WO ₃ , Rb _{0 . 33} WO ₃ , K _0.33 WO ₃ , Ba _{0 . 33} WO ₃ and the like, and Cs _{0 . 33} WO ₃ and Rb _{0 . 33} WO ₃ is preferred, and Cs _{0 . 33} WO ₃ is more preferred.

[B] The infrared shielding agent is preferably fine particles. [B] The upper limit of the average particle diameter (D50) of the 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 size is equal to or less than the above upper limit, the visible light transmittance can be further improved. On the other hand, from reasons such as ease of handling at the time of production, the average particle diameter of the [B] infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

The [B] infrared shielding agent can be synthesized by a known method, but is available as a commercial item. When 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 the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. The tungsten oxide-based compound is also available as a dispersion of tungsten fine particles, such as "YMF-02" from Sumitomo Kinzoku Kozan Co., Ltd., for example.

The lower limit of the content of the [B] infrared shielding agent in the total solid content in the composition is preferably 1% by mass, more preferably 5% by mass, and still more preferably 10% by mass. As for the lower limit of this content, 20 mass % is further more preferable, and 30 mass % is more preferable. On the other hand, as an upper limit of this content, 70 mass % is preferable, 65 mass % is more preferable, and 60 mass % is still more preferable. [B] By setting the content of the infrared shielding agent within the above range, the visible light transmittance and infrared shielding properties of the resulting optical filter are more well balanced.

The lower limit of the mass ratio ([B]/[A]) of the content of the [B] infrared shielding agent to the content of the [A] phthalocyanine compound is preferably 2, preferably 3, more preferably 5, and still more preferably 10. On the other hand, as an upper limit of this mass ratio ([B]/[A]), 40 is preferable, 30 is more preferable, and 20 is still more preferable. When the content ratio of the [A] phthalocyanine compound and the [B] infrared shielding agent falls within the above range, the visible light transmittance and infrared shielding properties of the resulting optical filter are more well balanced.

([C] Dispersant)

It is preferable that the said composition further contains the [C] dispersing agent. The [C] dispersant improves the uniform dispersibility of the [B] infrared shielding agent (particularly, a metal oxide), and further enhances the visible light transmittance and infrared ray shielding properties of the obtained optical filter.

Examples of the [C] dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, (meth)acrylic dispersants, and the like. Among these, a (meth)acrylic dispersing agent is preferable. [C] It is preferable that a dispersing agent is a block copolymer.

[C] The dispersant is commercially available, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, manufactured by BYK) as a (meth)acrylic dispersant, and Disperbyk-161, Disperbyk-162, and Disperbyk- as a urethane dispersant. 165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above, manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) as a polyethylene imine dispersant, Ajisper PB821, Ajisper as a polyester dispersant PB822, Ajisper PB880, Ajisper PB881 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), as well as BYK-LPN21324 (manufactured by Big Chemie (BYK)) and the like.

[C] The lower limit of the amine value of the dispersing agent is preferably 10 mgKOH/g, more preferably 40 mgKOH/g, still more preferably 80 mgKOH/g. On the other hand, as an upper limit of this amine value, 300 mgKOH/g is preferable, 200 mgKOH/g is more preferable, and 150 mgKOH/g is still more preferable. By using a dispersant having such an amine value, the dispersibility of the [B] infrared shielding agent is improved, and the visible light transmittance and infrared shielding properties of the resulting optical filter can be further improved. In addition, "amine value" is the mg number of KOH equivalent to HCl required to neutralize 1g of solid content of a dispersing agent.

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

([D] polymerizable compound)

It is preferable that the said composition further contains [D] polymeric compound. When the composition contains the [D] polymerizable compound, good curability and good heat resistance of the resulting optical filter can be exhibited. [D] The polymerizable compound refers to a compound having two or more polymerizable groups. As a group which can superpose|polymerize, an ethylenically unsaturated group, oxiranyl group, oxetanyl group, N-alkoxymethylamino group etc. are mentioned, for example. [D] As the polymerizable compound, a compound having two or more (meth)acryloyl groups and a compound having two or more N-alkoxymethylamino groups are preferable, and a compound having two or more (meth)acryloyl groups is more preferable. [D] The polymerizable compound can be used alone or in combination of two or more.

Examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate, which is a reaction product of (meth)acrylate having a hydroxyl group and polyfunctional isocyanate, (meth)acrylate and an acid anhydride having a hydroxyl group; polyfunctional (meth)acrylates having a carboxyl group, etc., which are reactants of

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol dimethacrylate. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate etc. are mentioned, for example. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

Specific examples of the compound having two or more (meth)acryloyl groups include, for example, ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and bisphenoxyethanol fluorene. Di(meth)acrylate, dimethyloltricyclodecanedi(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropylmethacrylate, 2-(2'-vinyloxyethoxy)ethyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, urethane (meth)acrylate compounds, and the like.

Among the compounds having two or more (meth)acryloyl groups, polyfunctional (meth)acrylates are preferable, and polyfunctional (meth)acrylates having 3 or more and 10 or less (meth)acryloyl groups are more preferable. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds 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'-tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, and the like.

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

([E] polymerization initiator)

It is preferable that the said composition contains [E] polymerization initiator. [E] Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but a photopolymerization initiator is preferable. Thereby, photosensitivity (radiation sensitivity) can be provided to the said composition. A photopolymerization initiator refers to a compound that generates an active species capable of initiating polymerization of the [D] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, or X-ray. [E] A polymerization initiator can be used 1 type or in mixture of 2 or more types.

Examples of the polymerization initiator [E] include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and onium salt compounds. Among these, thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyloxime-based compounds are preferred, and O-acyloxime-based compounds are more preferred.

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

Examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

As the biimidazole compound, 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-trichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole etc. are mentioned.

Moreover, when using a biimidazole type compound, it is preferable to use a hydrogen donor together from the point which can improve sensitivity. A "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and amine hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Examples of the triazine-based compound include compounds described in paragraphs [0063] to [0065] of Japanese Patent Publication No. 57-6096 and Japanese Unexamined Patent Publication No. 2003-238898.

Examples of O-acyloxime compounds include 1,2-octanedion-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl). -9H-carbazol-3-yl] -1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like. As commercially available products of O-acyloxime compounds, NCI-831 and NCI-930 (above, manufactured by ADEKA Corporation), OXE-03 and OXE-04 (above, manufactured by BASF) and the like can also be used.

When using a photoinitiator, a sensitizer can also be used together. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, and 7-diethylamino-3-(4-di). Ethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc. are mentioned.

The lower limit of the content of the [E] polymerization initiator is preferably 1 part by mass and more preferably 5 parts by mass with respect to 100 parts by mass of the polymerizable compound [D]. On the other hand, as an upper limit of this content, 100 mass parts is preferable and 20 mass parts is more preferable.

(binder resin)

The composition may further contain binder resin. Although it does not specifically limit as binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxy group and a phenolic hydroxyl group. Especially, the polymer which has a carboxy group (henceforth a "carboxy group containing polymer") is preferable. Examples of the carboxy group-containing polymer include copolymers of an ethylenically unsaturated monomer having at least one carboxy group (hereinafter also referred to as “unsaturated monomer (1)”) and another copolymerizable ethylenically unsaturated monomer (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-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, and p-vinylbenzoic acid.

As the unsaturated monomer (2), for example

N-position substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) ) Acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0^2,6]decan-8-yl(meth)acrylate, dicyclopentenyl(meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, paracumylphenol ethylene oxide modified (meth)acrylate, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl (meth)acrylic acid esters such as ]-3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane,

and macromonomers having mono(meth)acryloyl groups at terminals of polymer molecular chains, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

Moreover, as binder resin, you can also use the carboxyl group containing polymer which has polymerizable unsaturated bonds, such as a (meth)acryloyl group, in a side chain. Moreover, polysiloxane etc. can also be used as binder resin.

When the said composition contains binder resin, content of binder resin can be 10 mass parts or more and 10,000 mass parts or less normally with respect to 100 mass parts of [A] phthalocyanine compounds.

(additive)

The said composition may contain various additives as needed.

Examples of additives include surfactants, adhesion accelerators, antioxidants, ultraviolet absorbers, aggregation inhibitors, residue improvers, and developability improvers.

As surfactant, a fluorosurfactant, silicone surfactant, etc. are mentioned. As content of surfactant, it can be 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] phthalocyanine compounds normally.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Examples of antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2, 4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and the like. As content of antioxidant, it can be set as 0.01 mass part or more and 10 mass parts or less normally with respect to 100 mass parts of [A] phthalocyanine compounds.

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

As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

Examples of the residue improving agent include malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 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 improving agent include succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, and the like.

(Other organic pigments, etc.)

The composition may contain known organic dyes other than organic dyes as [A] a phthalocyanine compound and [B] a copper compound that is an infrared ray shielding agent. Examples of other organic dyes include diiminium compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quaterrylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexapyrine compounds and the like (excluding those containing copper atoms). Moreover, [A] phthalocyanine compounds and [B] phthalocyanine compounds other than phthalocyanine compounds as infrared ray shielding agents can also be used.

Moreover, it is preferable to use together [A] phthalocyanine compound and [A] phthalocyanine compounds other than a phthalocyanine compound (it is also hereafter called "[a] phthalocyanine compound"). [a] The lower limit of the maximum absorption wavelength of the phthalocyanine compound is preferably 600 nm, more preferably 650 nm, still more preferably 700 nm, still more preferably 750 nm, and even more preferably 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, in some cases even more preferably 800 nm, in some cases even more preferably 750 nm, in some cases even more preferably 700 nm. [A] The lower limit of the difference between the maximum absorption wavelength of the phthalocyanine compound and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm, and even more preferably 50 nm in some cases. On the other hand, the upper limit of this difference is preferably 100 nm, more preferably 80 nm, and even more preferably 50 nm in some cases. By using such a phthalocyanine compound in combination, the visible light transmittance and infrared ray shielding properties of the obtained optical filter can be further improved. In addition, the visible light uniform transmittance of the obtained optical filter can be improved. [a] A phthalocyanine compound also includes a [B] phthalocyanine compound as a copper compound that is an infrared ray shielding agent. [a] As for the phthalocyanine compound, conventionally well-known various phthalocyanine compounds are mentioned.

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, more preferably 80% by mass, sometimes more preferably 90% by mass, sometimes more preferably 99% by mass. As an organic dye, there are cases where it is preferable to substantially contain only the [A] phthalocyanine compound. The composition can increase productivity by reducing the content of other organic dyes in this way. In addition, uniform transmission of visible light in the resulting optical filter can be improved.

In addition, as the number of types of organic dyes contained in the composition, including the [A] phthalocyanine compound, 3 types or less are preferable, 2 or less types are more preferable, and 1 type is more preferable in some cases. Even when the number of types of organic dyes contained in this way is reduced, the productivity can be increased and the uniform transmittance of visible light in the resulting optical filter can also be improved. Moreover, when using 2 or more types of organic dyes, it is preferable to use [A] phthalocyanine compound and [A] phthalocyanine compounds other than a phthalocyanine compound together.

(menstruum)

The composition is usually prepared as a liquid composition containing a solvent (dispersion medium). As the solvent, it can be appropriately selected and used as long as it disperses or dissolves other components, does not react with these components, and has suitable volatility.

As such a solvent, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene 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, (poly)alkylene glycol monoalkyl ethers such as 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, and tripropylene glycol monoethyl ether;

lactate alkyl esters such as methyl lactate and ethyl lactate;

(cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, and cyclohexanol;

keto alcohols such as diacetone alcohol;

(poly)alkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Len glycol monoalkyl ether acetates,

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

ketones such as chain ketones such as methyl ethyl ketone, 2-heptanone and 3-heptanone, and cyclic ketones such as cyclopentanone and cyclohexanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoate Other esters such as

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone

etc. can be mentioned.

The content of the solvent in the composition is not particularly limited. The lower limit of the solid content concentration (total concentration of each component excluding the solvent) in the composition is preferably 5% by mass and more preferably 10% by mass. On the other hand, as an upper limit of this solid content concentration, 50 mass % is preferable and 40 mass % is more preferable. By setting the solid content concentration within the above range, dispersibility, stability, coatability, and the like become better.

(preparation method)

It does not specifically limit as a preparation method of the said composition, It can prepare and adjust by mixing each component. For example, when the composition contains [B] a metal oxide as an infrared shielding agent, and [C] a dispersing agent, first, a method of preparing a dispersion containing [B] an infrared shielding agent, [C] a dispersing agent, and a solvent, adding [A] a phthalocyanine compound and other components to the dispersion, and mixing them can be adopted. The dispersion or the composition may be subjected to a filtration treatment as necessary to remove aggregates.

<Infrared ray shielding film (I)>

An infrared shielding film (I) according to an embodiment of the present invention is an infrared shielding film for a solid-state imaging device formed from the composition for a solid-state imaging device. The optical filter for a solid-state imaging device having the infrared shielding film (I) has both good visible light transmittance and infrared shielding properties even when the number of organic dyes contained is small. In addition, the infrared shielding film (I) has excellent uniform transmittance in the visible light region.

The infrared shielding film (I) is preferably incorporated into a solid-state imaging device as a constituent member. In this case, the infrared shielding film (I) alone functions as an optical filter (infrared cutoff filter). By incorporating the infrared shielding film (I) into the solid-state imaging device, a large process margin can be obtained, which is preferable. When the infrared shielding film (I) is incorporated in a 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 element, between the microlens and the color filter, between the color filter and the photodiode, and the like. The infrared shielding film (I) is preferably laminated between a microlens and a color filter or between a color filter and a photodiode.

As said optical filter, the said infrared shielding film (I) may be laminated|stacked on the surface of a transparent substrate. As the transparent substrate, glass, transparent resin, or the like is employed. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Such an optical filter is also suitably used as an infrared cut-off filter or the like in a solid-state imaging device.

A solid-state imaging device including the optical filter is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, monitoring cameras, automobile cameras, portable information terminals, personal computers, video games, medical equipment, and the like.

The said infrared shielding film (I) can be formed by the following method, for example. First, after apply|coating the said composition on a support body, prebaking is performed and a solvent is evaporated and a coating film is formed. Next, after exposing this coating film, it develops using a developing solution, and the unexposed part of the coating film is dissolved and removed. After that, by post-baking, the infrared shielding film (I) patterned into a predetermined shape is obtained. In addition, when the said composition does not contain [D] polymeric compound and [E] polymerization initiator, it is not necessary to perform hardening treatment, such as exposure. Moreover, it is not necessary to perform a developing process, and in this case, an unpatterned infrared shielding film (I) can be formed.

Examples of the support to which the composition is applied include the transparent substrate, microlens, and color filter. For the coating, an appropriate 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 can be employed.

Conditions for heat drying in the prebaking are, for example, 70°C or more and 110°C or less, about 1 minute or more and 10 minutes or less.

Examples of the light source for radiation used for exposure of the coating film include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, and laser light sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. As an exposure light source, an ultraviolet LED can also be used. As for the wavelength, the radiation in the range of 190 nm or more and 450 nm or less is preferable. The exposure amount of radiation is generally about 10 J/m ² or more and 50,000 J/m ² or less.

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

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid pool) developing method, or the like can be applied. The developing conditions are about 5 seconds or more and 300 seconds or less at room temperature.

As conditions for post-baking, they are usually 180°C or more and 280°C or less, about 1 minute or more and 60 minutes or less.

The lower limit of the average film thickness of the infrared shielding film (I) thus formed is usually 0.5 μm, preferably 1 μm. On the other hand, as an upper limit of this average film thickness, it is 5 micrometers normally, and 3 micrometers is preferable. When the average film thickness of the infrared shielding film (I) is within the above range, the balance between the visible light transmittance and the infrared shielding performance is better. In addition, as for the suitable visible light transmittance and infrared transmittance of the infrared shielding film (I), the range of the infrared shielding film (II) described later can be applied.

<Infrared ray shielding film (II)>

An infrared shielding film (II) according to an embodiment of the present invention is an infrared shielding film for a solid-state imaging device that substantially contains only one or two organic dyes and satisfies the following (A) to (C).

(A) The average value of the transmittance in the wavelength range of 430 nm or more and 580 nm or less is 75% or more

(B) The average value of the transmittance in the wavelength range of 700 nm or more and 900 nm or less is 16.5% or less

(C) transmittance of 10% or less at a wavelength of 1200 nm

An optical filter for a solid-state imaging device provided with the infrared shielding film (II) has both good visible light transmittance and infrared shielding properties. Moreover, since the said infrared shielding film (II) contains substantially only 1 type or 2 types of organic dyes, preparation is easy and productivity is high. Here, "substantially containing only 1 type or 2 types of organic dyes" means that the content rate of 1 type or 2 types of organic dyes occupied by all the organic dyes contained is 90 mass % or more. It is preferable that it is 99 mass % or more, and, as for this content rate, it is more preferable that it is 99.9 mass % or more. It is preferable that the said infrared shielding film (II) contains only one organic dye substantially.

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

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

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

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

(C) Although the upper limit of the transmittance|permeability in wavelength 1200nm is 10 %, 8 % is preferable, 7 % is more preferable, and 6.1 % is still more preferable. When this transmittance is below the said upper limit, favorable infrared ray shielding property can be exhibited. On the other hand, the lower limit of this 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 expressed by the following formula is 10% or less

As for the upper limit of the said visible light uniform transmittance, 9 % is more preferable, and 8 % is still more preferable. When the visible light uniform transmittance is equal to or less than the above upper limit, the transmittance of visible light is uniformed, and better visibility correction can be performed. The lower limit of the visible light uniform transmittance is not particularly limited, and may be, for example, 1%, 3%, or 5%.

Uniform visible light transmittance = {(average value of transmittance in the range of wavelength 430 nm to 580 nm - lowest value of transmittance in the range of wavelength 430 nm to 580 nm) / average value of transmittance in the range of wavelength 430 nm to 580 nm} × 100 (%)

The said infrared shielding film (II) can be formed, for example from the composition for solid-state image sensor which is an embodiment of this invention mentioned above. The method for forming the infrared shielding film (II) is also the same as the method described above as the method for forming the infrared shielding film (I). However, in the said composition to be used, substantially only 1 type or 2 types of organic dyes are contained, and at least [A] phthalocyanine compound corresponds to an organic dye. That is, in the said infrared shielding film (II), it is preferable that the said organic dye is a phthalocyanine compound ([A] phthalocyanine compound) represented by said Formula (1).

A preferable form of the composition for solid-state imaging devices for forming the infrared shielding film (II) is also the same as the composition for solid-state imaging devices described above. That is, it is preferable that the said infrared shielding film (II) further contains the infrared shielding agent ([B] infrared shielding agent) which is a metal oxide, a copper compound, or a combination thereof. Further, it is preferable that the [B] infrared shielding agent is cesium tungsten oxide. Other preferred forms of the infrared shielding film (II) are also the same as those of the infrared shielding film (I) formed from the composition for a solid-state imaging device.

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

<Solid-state imaging device>

A solid-state imaging device according to an embodiment of the present invention is a solid-state imaging device having the infrared shielding film (I) or the infrared shielding film (II). Since the solid-state imaging device has an infrared shielding film having both good visible light transmittance and infrared shielding properties even when the number of organic dyes contained is small, good visibility correction is achieved.

The solid-state imaging device generally has a structure in which a layer in which a plurality of photodiodes are disposed, a color filter, and a microlens are laminated in this order. In addition, a flattening layer may be provided between these layers. In the solid-state imaging device, light enters from the microlens side. The incident light passes through the microlens and the color filter and reaches the photodiode. In addition, as for the color filters, for example, in each of the R (red), G (green), and B (blue) filters, only light in a specific wavelength range is configured to transmit.

In the solid-state imaging device, the infrared shielding film (I) or the infrared shielding film (II) may be provided on the outer surface side of the microlens, between the microlens and the color filter, between the color filter and a layer on 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 a microlens and a color filter or between a color filter and a photodiode. In addition, another layer (flattening layer or the like) may be further provided between the infrared shielding film (I) or the infrared shielding film (II) and the microlens, color filter, photodiode, or the like.

As a specific example of the said solid-state imaging element, CCD, CMOS, etc. as a camera module are mentioned. The solid-state imaging device is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, monitoring cameras, automobile cameras, personal digital assistants, personal computers, video games, medical equipment, and the like.

[Example]

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

<Synthesis Example 1>

According to the above Scheme 1, a phthalocyanine compound (A-1) (maximum absorption wavelength 735 nm) represented by the following formula was synthesized. As a starting material, 1,2-dicyano-3,6-di(4-methoxybutyl)benzene was used. "One. As the base”, lithium pentoxide (solid lithium and pentan-1-ol) was used, and “2. As "acid", glacial acetic acid was used. In addition, as a salt imparting M ²⁺ , a vanadyl salt was used.

<Synthesis Example 2>

A phthalocyanine compound (a-1) represented by the following formula (maximum absorption wavelength: 692 nm) was synthesized using the method described in paragraphs [0020] to [0025] (Example 1) of JP-A-05-25177.

<Synthesis Example 3>

A phthalocyanine compound (a-2) represented by the following formula (maximum absorption wavelength: 728 nm) was synthesized using the method described in paragraph [0075] (Example 4) of JP-A-2016-204536.

In addition, the pigment|dye used is as follows.

・Compound (a-3): "FDN-002" from Yamada Chemical Industry Co., Ltd. (phthalocyanine compound: maximum absorption wavelength 807 nm)

<Synthesis Example 4>

Cesium tungsten oxide (Cs _0.33 WO ₃ ) powder was synthesized using the method described in paragraph [0113] of Japanese Patent No. 4096205.

[Production Example]

25.00 parts by mass of the above cesium tungsten oxide, 13.11 parts by mass of "BYK-LPM6919" (solid content concentration 61% by mass, amine value 120 mgKOH/g) by Big Chemie as a dispersing agent, and 61.89 parts by mass of cyclopentanone (CPN) as a solvent (dispersion medium) 61.89 parts by mass were prepared. These were filled in a container together with 2000 parts by mass of 0.1 mm diameter zirconia beads and dispersed in a paint shaker to obtain a dispersion having an average particle diameter (D50) of 19 nm. In addition, the average particle diameter was measured by the DLS method using a light scattering measuring device ("ALV-5000" manufactured by ALV, Germany).

[Example 1]

50.00 parts by mass of the dispersion, 0.75 parts by mass of a phthalocyanine compound (A-1), 7.01 parts by mass of "KAYARAD DPHA" (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku as a polymerizable compound, and 0.70 parts by mass of "NCI-930" (O-acyloxime compound) manufactured by ADEKA as a polymerization initiator; 0.02 parts by mass of "FTX-218D" (fluorine-based surfactant) manufactured by Neos as a surfactant, 0.01 part by mass of "Irganox 1010" (phenolic antioxidant) manufactured by BASF as an antioxidant, and 41.50 parts by mass of cyclopentanone (CNP) as a solvent were weighed into a container and mixed with a stirrer. The composition of Example 1 was obtained by filtering 200 mL of this mixture under pressure at 0.5 MPa for 3 minutes using a 0.5 µm PTFE (polytetrafluoroethylene) filter.

[Examples 2 to 3, Comparative Examples 1 to 3]

Each composition of Examples 2-3 and Comparative Examples 1-3 was obtained in the same manner as in Example 1, except that the composition of each component was set as shown in Table 1.

[evaluation]

The following evaluation was performed using each obtained composition. Table 1 shows the evaluation results.

Each composition was applied on a glass substrate by spin coating to a predetermined film thickness. After that, the coating film was heated at 100°C for 120 seconds, and exposed using an i-line stepper to 1000 mJ/cm ² . Subsequently, by heating at 220°C for 300 seconds, an infrared shielding film having an average film thickness of 1.4 to 1.6 µm was produced on the glass substrate. Each average film thickness is shown in Table 1. In addition, the film thickness was measured with a stylus step meter ("α Step IQ" by Yamato Chemical Co., Ltd.). Next, the transmittance in each wavelength region of the infrared shielding film prepared on the glass substrate was measured in comparison with the glass substrate using a spectrophotometer ("V-7300" manufactured by Nippon Bunko Co., Ltd.). From the obtained spectrum, evaluation was performed according to the following evaluation criteria. In addition, the transmission spectrum of the infrared shielding film of Example 1 is shown in FIG. In the transmission spectrum of Fig. 1, the abscissa is the wavelength (nm), and the ordinate is the transmittance (%).

(visible light transmittance)

An average transmittance of 430 to 580 nm was calculated. When the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film decreases. In addition, the average transmittance was evaluated according to the following criteria.

A: 80% or more

B: 70% or more and less than 80%

C: less than 70%

(Infrared ray shielding 1)

An average transmittance of 700 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. In addition, the average transmittance was evaluated according to the following criteria.

A: less than 15%

B: 15% or more and less than 20%

C: 20% or more

(Infrared ray shielding 2)

Regarding the transmittance at a wavelength of 1200 nm, the transmittance is less than 15%, and it can be said that the infrared shielding property is good for practical use. The transmittance at a wavelength of 1200 nm was evaluated according to the following criteria.

A: less than 10%

B: 10% or more and less than 15%

C: 15% or more

(S/N ratio)

Practical performance was estimated by taking the ratio (S/N ratio) of the average transmittance (S) of the visible region (430 to 580 nm) and the average transmittance (N) of the infrared region (700 to 900 nm). The higher the S/N ratio, the better the performance, and when it was 5 or more, it was judged to be at a practical level and usable. The S/N ratio was evaluated according to the following criteria.

A: 5 or more

B: less than 5

(visible light uniform transmittance)

From the average transmittance (S) in the visible light region (430 to 580 nm) and the minimum transmittance (S _min ) in the visible light region, X (uniform visible light transmittance) was obtained based on the following formula, and uniform transmittance of visible light was evaluated.

X = ((SS _min ) / S) × 100 (%)

It can be judged that the smaller X is, the higher the uniform transmittance of visible light is. About the said X, it was evaluated according to the following criteria.

A: less than 10%

B: 10% or more

As shown in Table 1, the infrared shielding films of Examples 1 to 3 have good visible light transmittance and infrared shielding properties (A or B), and are also excellent in uniform transmittance of visible light. In addition, it is understood that the infrared shielding films of Examples 1 to 3 can express such good characteristics even though the organic dye-containing species are one or two.

The composition for solid-state imaging devices of the present invention can be suitably used as a forming material for an optical filter of a solid-state imaging device, more specifically, an infrared filter or the like.

Claims (15)

A phthalocyanine compound represented by the following formula (1)
A composition for a solid-state imaging device containing a.

(In formula (1), a plurality of R's are each independently an alkyl group or an aryl group. A plurality of X's are each independently a hydrogen atom, a halogen atom, or an alkyl group. A plurality of X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. A plurality of n's are each independently an integer of 3 to 6.) The infrared shielding agent of claim 1, which is a metal oxide, a copper compound (excluding the phthalocyanine compound) or a combination thereof.
A composition for a solid-state imaging device further comprising. The composition for a solid-state imaging device according to claim 2, wherein the infrared ray shielding agent is cesium tungsten oxide. The composition for a solid-state imaging device according to claim 2, wherein the content of the metal oxide, the copper compound, or a combination thereof is 1% by mass or more and 70% by mass or less with respect to the total solid content. The composition for solid-state imaging devices according to claim 1, wherein the content of the phthalocyanine compound is 0.1% by mass or more and 30% by mass or less with respect to the total solid content. The composition for a solid-state imaging device according to claim 1, wherein R in the formula (1) is a linear or branched alkyl group having 1 to 12 carbon atoms. The composition for a solid-state imaging device according to claim 1, wherein M in Formula (1) is H ₂ , Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO or TiO. An infrared shielding film for a solid-state imaging device formed from the composition for a solid-state imaging device according to any one of claims 1 to 7. An infrared shielding film for a solid-state imaging device that substantially contains only one or two organic dyes, satisfies the following (A) to (C), and the organic dye is a phthalocyanine compound represented by the following formula (1).
(A) The average value of the transmittance in the wavelength range of 430 nm or more and 580 nm or less is 75% or more
(B) The average value of the transmittance in the wavelength range of 700 nm or more and 900 nm or less is 16.5% or less
(C) transmittance of 10% or less at a wavelength of 1200 nm

(In formula (1), a plurality of R's are each independently an alkyl group or an aryl group. A plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal derivative. A plurality of n's are each independently an integer of 3 to 6.) The infrared shielding film according to claim 9, wherein (D) the visible light uniform transmittance expressed by the following formula is 10% or less.
Uniform visible light transmittance = {(average value of transmittance in the range of wavelength 430 nm to 580 nm - lowest value of transmittance in the range of wavelength 430 nm to 580 nm) / average value of transmittance in the range of wavelength 430 nm to 580 nm} × 100 (%) 10. The infrared shielding agent of claim 9, which is a metal oxide, a copper compound, or a combination thereof.
An infrared shielding film further comprising. The infrared shielding film according to claim 11, wherein the infrared shielding agent is cesium tungsten oxide. delete A solid-state imaging device comprising the infrared shielding film according to claim 8. A solid-state imaging device comprising the infrared shielding film according to any one of claims 9 to 12.