JP2018180167A - Composition for solid state image sensors, infrared-shielding film and solid state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for solid state image sensors that can form an optical filter for solid state image sensors having both excellent visible light transmitting and infrared-shielding properties even when the composition only contains limited kinds of organic dyes.SOLUTION: A composition for solid state image sensors contains a phthalocyanine compound having a transmission spectrum represented by Figure 1.SELECTED DRAWING: Figure 1

Description

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

  Solid-state imaging devices such as a CCD (Charge-Coupled Device) image sensor and a CMOS (Complementary MOS) image sensor are mounted on a video camera, a digital camera, a mobile phone with a camera function, and the like. The sensitivity of the photodiodes provided in these solid-state imaging devices ranges from the visible light range to the infrared range. For this reason, in the solid-state imaging device, a filter for blocking infrared rays is provided. The infrared blocking filter can correct the sensitivity of the solid-state imaging device so as to approach human visibility.

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

  However, even in the conventional infrared blocking filter using a phthalocyanine compound, the visible light transmitting property and the infrared shielding property are not sufficiently satisfied. Therefore, in order to exhibit the above-mentioned good properties, for example, many kinds of infrared shielding agents may be mixed and used. The use of such a large number of infrared shielding agents is also a factor causing high cost and reduced productivity. Moreover, in the conventional infrared blocking filter using a phthalocyanine compound, the dispersion | variation in the transmittance | permeability may be large in visible region. Also in such a case, good visibility correction will not be made.

JP, 2008-20195, A

  However, even in the case of an infrared blocking filter for a conventional solid-state imaging device using a phthalocyanine compound, the visible light transmitting property and the infrared shielding property are not sufficiently satisfied. Therefore, in order to exhibit the above-mentioned good properties, for example, many kinds of infrared shielding agents may be mixed and used. The use of such a large number of infrared shielding agents is also a factor causing high cost and reduced productivity. Moreover, in the conventional infrared blocking filter using a phthalocyanine compound, the dispersion | variation in the transmittance | permeability may be large in visible region. Also in such a case, good visibility correction will not be made.

  The present invention has been made based on the above circumstances, and the object thereof is to have both good visible light transmission and infrared shielding properties even when the type of the organic dye contained is small. A composition for a solid-state imaging device capable of forming an optical filter for a solid-state imaging device, solid-state imaging having both excellent visible light transparency and infrared shielding properties even if the type of organic dye contained is small An infrared shielding film for a device, and a solid-state imaging device having such an infrared shielding film.

（式（１）中、複数のＲは、それぞれ独立して、アルキル基又はアリール基である。複数のＸは、それぞれ独立して、水素原子、ハロゲン原子又はアルキル基である。複数のＸは、互いに結合してこれらが結合する炭素鎖と共に芳香環を形成していてもよい。Ｍは、２つの水素原子、２価の金属原子、又は３若しくは４価の金属原子の誘導体である。複数のｎは、それぞれ独立して、３〜６の整数である。） The invention made in order to solve the above-mentioned subject is a composition for solid imaging devices containing the phthalocyanine compound (Hereafter, it is also called "[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 is M 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. Each n is independently an integer of 3 to 6)

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

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

  Another invention made in order to solve the above-mentioned subject is a solid-state image sensing device which has the infrared shielding film (I) or the infrared shielding film (II).

  According to the present invention, a solid-state imaging device capable of forming an optical filter for a solid-state imaging device having both excellent visible light transparency and infrared shielding properties even when the type of organic dye contained is small Composition, an infrared shielding film for a solid-state imaging device having both good visible light transmittance and infrared shielding properties even when the type of the organic pigment contained is small, and such an infrared shielding film A solid-state imaging device can be provided.

FIG. 1 is a transmission spectrum of the infrared shielding film of Example 1.

  Hereinafter, the composition for a solid-state imaging device, the infrared shielding film, and the 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 a solid-state imaging device (hereinafter, also simply referred to as a “composition”) according to an embodiment of the present invention contains an [A] phthalocyanine compound. It is preferable that the said composition further contains the [B] infrared rays shielding agent which is a metal oxide, copper compounds (except [A] phthalocyanine compound), or these combination.

([A] phthalocyanine compound)
[A] The phthalocyanine compound is a compound represented by the following formula (1). [A] The phthalocyanine compound has high transparency in the visible light range (eg, a wavelength range of 430 nm to 580 nm), and high shielding properties in the near infrared range (eg, a wavelength range of 700 nm to 900 nm). Since the composition contains such [A] phthalocyanine compound, it forms an optical filter having both good visible light transmittance and infrared shielding properties even when the type of the organic dye contained is small. can do. Moreover, since the said composition contains such [A] phthalocyanine compound, it can form an optical filter with high uniform transmittance | permeability in visible region.

  In Formula (1), a plurality of R's are each independently an alkyl group or an aryl group. The plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X may be bonded to each other to form an aromatic ring 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. Each of the plurality n is independently an integer of 3 to 6.

  Examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group A C1-C30 linear or branched alkyl group can be mentioned.

  As an aryl group represented by said R, a phenyl group, a tolyl group, xylyl group, a naphthyl group, an anthracenyl group etc. can be mentioned.

  As said R, an alkyl group is preferable and a C1-C12 linear or branched alkyl group is more preferable. Further, the upper limit of the carbon number of the alkyl group is preferably 6, more preferably 4, and still more preferably 2. 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. can be mentioned.

  As an alkyl group represented by said X, what was illustrated as an alkyl group represented by said R can be mentioned.

  Multiple X's may be joined together. Usually, among a plurality of X's, two X's bonded to the same benzene ring are bonded to each other to 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. can be mentioned. The hydrogen atom of these aromatic rings may be substituted by a hydrocarbon group or another substituent.

  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, Pb and the like. In addition, a bivalent metal atom means the metal atom which can become a bivalent cation.

Here, a derivative of a metal atom refers to an atom group containing a metal atom. The trivalent metal atom refers to a metal atom that can be a trivalent cation. Examples of trivalent metal atoms include Al and In. The tetravalent metal atom refers to a metal atom that can be a tetravalent cation. Si, Ge, Sn etc. can be mentioned as a tetravalent metal atom. The metal atom also includes a semimetal atom. As derivatives of the trivalent or tetravalent metal atom represented by M, AlCl, AlBr, AlI, AlOH, InCl, InBr, InBr, InI, InOH, SiCl ₂ , SiBr 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 M, H ₂ (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO and TiO are preferable, and VO is more preferable.

  The lower limit of the above n is preferably 4. As an upper limit of said n, 5 is preferable and 4 is more preferable.

  The lower limit of the maximum absorption wavelength of the [A] phthalocyanine compound is preferably 680 nm, more preferably 700 nm, and still more preferably 720 nm. On the other hand, the upper limit of the 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 in the above range, it is possible to form an optical filter having both better visible light transmittance and infrared shielding properties.

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

  In scheme 1, R, X, M and n are as defined in the formula (1).

In addition, as a dicyano compound in the above-mentioned scheme 1, a plurality of dicyano compounds different in the substituent (RO (CH ₂ ) _n -or X) may be used. Sources of metal ions and the like 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 the 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 -Methyl pyrrolidone, dioxane, alcohol (methanol, ethanol etc.) etc. can be mentioned.

  The lower limit of the content of the [A] phthalocyanine compound in the total solid content in 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, the upper limit of the content is preferably 30% by mass, more preferably 15% by mass, still more preferably 10% by mass, and still more preferably 5% by mass. [A] By setting the content of the phthalocyanine compound in the above-mentioned range, the visible light transmittance and the infrared ray shielding property of the optical filter to be obtained are in better 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 one or two types of [A] phthalocyanine compounds, and it is more preferable to use only one type of [A] phthalocyanine compound. [A] The phthalocyanine compound can exhibit good visible light transmission and infrared shielding properties only by one kind. Therefore, by reducing the number of types of the [A] phthalocyanine compound used, productivity can be enhanced while exhibiting good visible light transmittance and infrared shielding properties.

([B] Infrared shielding agent)
[B] The 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 to 2000 nm 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] As metal oxides as infrared shielding agents, for example, 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 ), etc. can be mentioned.

  [B] Examples of copper compounds as infrared shielding agents include copper phthalocyanine compounds and other copper complexes. Examples of copper phthalocyanine compounds include copper phthalocyanine, chlorinated copper phthalocyanine, chlorinated brominated copper phthalocyanine, brominated copper phthalocyanine and the like.

  [B] The infrared shielding agent is preferably a metal oxide, more preferably a tungsten oxide compound. Tungsten oxide-based compounds are infrared shielding agents that have high absorption for infrared light (in particular, infrared light having a wavelength of about 800 nm to 1200 nm) (that is, high shielding ability for infrared light) and low absorption for visible light. is there. Therefore, when the said composition contains a tungsten oxide type compound, infrared rays shielding property can be improved, maintaining the favorable visible light permeability of the optical filter obtained. [B] An infrared shielding agent may be used individually by 1 type, and may mix and use 2 or more types.

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

  In Formula (2), A is a metal element. It is 0.001 <= x <= 1.1. It is 2.2 <= y <= 3.0.

  As a metal element represented by A in the said Formula (2), an alkali metal, alkaline-earth metal, 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. The metal element represented by A may be one kind or two or more kinds.

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

  When x in the above-mentioned 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 compound can be more reliably avoided. The upper limit of x is preferably 1 and more preferably 0.5.

  When y in the above formula (2) is 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, when y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the above formula (2) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ and Rb _0.33 WO ₃ are preferable, and Cs _0.33 WO ₃ is more preferable.

  [B] The infrared shielding agent is preferably in the form of fine particles. [B] The upper limit of the average particle size (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 less than or equal to the above upper limit, visible light transmission can be further enhanced. 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 easy handling at the time of production.

  [B] The infrared shielding agent can also be synthesized by a known method, but is commercially available. When the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained, for example, by a heat treatment of a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. In addition, a tungsten oxide based compound can be obtained, for example, as a dispersion of tungsten fine particles such as “YMF-02” manufactured by Sumitomo Metal Mining Co., Ltd.

  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. 20 mass% is still more preferable, and, as for the minimum of this content, 30 mass% is more preferable. On the other hand, as a maximum of this content, 70 mass% is preferred, 65 mass% is more preferred, and 60 mass% is more preferred. [B] By setting the content of the infrared shielding agent in the above range, the visible light transmittance and the infrared shielding property of the optical filter to be obtained are in a better balance.

  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, 3 is preferable, 5 is more preferable, and 10 is Even more preferable. On the other hand, the upper limit of the mass ratio ([B] / [A]) 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 in the above range, the visible light transmittance and the infrared shielding property of the optical filter to be obtained become a better balance.

([C] Dispersant)
The composition preferably further contains a [C] dispersant. [C] The dispersing agent can enhance the uniform dispersion of the [B] infrared shielding agent (particularly, metal oxide), and can further improve the visible light transmittance and the infrared shielding property of the obtained optical filter.

  [C] Dispersants include, for example, urethane type dispersants, polyethylene imine type dispersants, polyoxyethylene alkyl ether type dispersants, polyoxyethylene alkyl phenyl ether type dispersants, polyethylene glycol diester type dispersants, sorbitan fatty acid ester type Examples of the dispersant include polyester dispersants and (meth) acrylic dispersants. Among these, (meth) acrylic dispersants are preferable. [C] The dispersant is preferably a block copolymer.

  [C] Dispersants can be obtained commercially, and for example, as (meth) acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN 21116, BYK-LPN 22102 (all, BYK Chemie (BYK) Made as a urethane type dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk- 2164 (all by BIC Chemie (BYK)), Sols spars 76500 (Lublisol Co., Ltd.), Solsperse 24000 (Lubrisol Co., Ltd.) as a polyethyleneimine dispersant, polyester dispersion As, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (or, Ajinomoto Fine-Techno Co., Ltd.) Other, BYK-LPN21324 (Chemie (BYK) Co.), and the like.

  [C] The lower limit of the amine value of the dispersant is preferably 10 mg KOH / g, more preferably 40 mg KOH / g, and still more preferably 80 mg KOH / g. On the other hand, the upper limit of the amine value is preferably 300 mg KOH / g, more preferably 200 mg KOH / g, and still more preferably 150 mg KOH / g. By using the dispersant having such an amine value, the dispersibility of the [B] infrared shielding agent can be improved, and the visible light transmittance and the infrared shielding property of the obtained optical filter can be further enhanced. The “amine value” is the number of mg of KOH and the equivalent of HCl necessary to neutralize 1 g of the dispersant solids.

  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, 200 mass parts is preferred, as for the upper limit of this content, 100 mass parts is more preferred, and 60 mass parts is still more preferred.

([D] polymerizable compound)
It is preferable that the said composition further contains a [D] polymeric compound. When the said composition contains a [D] polymeric compound, the favorable heat resistance etc. of the favorable hardenability, the optical filter obtained, etc. can be exhibited. [D] A 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. [D] The polymerizable compound is preferably a compound having two or more (meth) acryloyl groups, and a compound having two or more N-alkoxymethylamino groups, and has two or more (meth) acryloyl groups Compounds are more preferred. [D] The polymerizable compound can be used singly or in combination of two or more.

  Examples of compounds having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates and caprolactone-modified polyfunctional (meth) acrylates, which are the reaction products of aliphatic polyhydroxy compounds and (meth) acrylic acid, etc. Alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of hydroxyl group-containing (meth) acrylate and polyfunctional isocyanate, etc., hydroxyl group-containing (meth) acrylate and acid anhydride And polyfunctional (meth) acrylates having a carboxyl group, which is a reaction product with the above.

  Here, as the above-mentioned aliphatic polyhydroxy compound, for example, a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Aliphatic polyhydroxy compounds having three or more valences can be mentioned. 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. Etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the above acid anhydrides include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, biphenyl tetracarboxylic acid, etc. Examples include tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic acid 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-hexanediol di (meth) acrylate, 1 9, 9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bis phenoxy ethanol fluo orange (meth) acrylate, dimethylol tricyclode Candi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropant (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol 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 can be mentioned.

  Among the compounds having two or more (meth) acryloyl groups, polyfunctional (meth) acrylates are preferable, and polyfunctional (meth) acrylates having three or more and ten 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 ′ ′, N ′ ′-hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.

  10 mass parts is preferable with respect to 100 mass parts of [A] phthalocyanine compounds, as for content of a [D] polymeric compound, 200 mass parts is more preferable, and 500 mass parts is further more preferable. On the other hand, the upper limit of the content is preferably 3,000 parts by mass, and more preferably 2,000 parts by mass.

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

  [E] As a polymerization initiator, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones Examples include a compound based on a compound, a polynuclear quinone compound, a diazo compound, an imidosulfonate compound and an onium salt compound. Among these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and O-acyloxime compounds are preferable, and O-acyloxime compounds are more preferable.

  Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2 And 4-diisopropyl thioxanthone etc. can be mentioned.

  As an acetophenone compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like can be mentioned.

  As a 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 There can be mentioned '-tetraphenyl-1,2'-biimidazole and the like.

  In addition, when using a biimidazole type compound, it is preferable to use a hydrogen donor together in that the sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound upon exposure. Examples of hydrogen donors include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like. Mention may be made of amine hydrogen donors.

  As a triazine type compound, the compound as described in stage-of Unexamined-Japanese-Patent No. 57-6096 and Unexamined-Japanese-Patent No. 2003-238898 can be mentioned, for example.

  As O-acyloxime compounds, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H And -carbazol-3-yl] -1- (O-acetyloxime) and the like can be mentioned. As commercially available products of O-acyloxime compounds, NCI-831, NCI-930 (above, made by ADEKA Co., Ltd.), OXE-03, OXE-04 (above, made by BASF Corporation), etc. may also be used. it can.

  When using a photoinitiator, a sensitizer can also be used together. Such sensitizers include, for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylamino Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It can be mentioned.

  The lower limit of the content of the polymerization initiator [E] 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 preferred, and 20 mass parts is more preferred.

(Binder resin)
The composition may further contain a binder resin. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxy group or a phenolic hydroxyl group. Among them, a polymer having a carboxy group (hereinafter, also referred to as a "carboxy group-containing polymer") is preferable. As the carboxy group-containing polymer, for example, ethylene copolymerizable with an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter, also referred to as "unsaturated monomer (1)") Copolymers with a polyunsaturated monomer (hereinafter, also referred to as "unsaturated monomer (2)") can be mentioned.

  Examples of the unsaturated monomer (1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) Acrylate, p-vinylbenzoic acid and the like can be mentioned.

Examples of the unsaturated monomer (2) include N-substituted maleimides such as N-phenyl maleimide and N-cyclohexyl maleimide,
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene and the like
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 2 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, polypropylene glycol (degree of polymerization 2 to 10) (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, ethylene oxide modified (meth) acrylate of paracumyl phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3- (Meth) acrylic esters such as [(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl oxetane,
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyl oxetane, etc. ,
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

  Moreover, as a binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in a side chain can also be used. Moreover, polysiloxane etc. can be used as a 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 composition can also contain various additives as needed.

  Examples of the additive include surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, residue improvers, developability improvers, and the like.

  As surfactant, a fluorine surfactant, a silicone surfactant, etc. can be mentioned. The content of the surfactant can be usually 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] phthalocyanine compound.

  As an adhesion promoter, 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) ethyltrimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

  As the antioxidant, 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, thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned. The content of the antioxidant can be generally 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] phthalocyanine compound.

  Examples of UV absorbers include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones.

  As an anticoagulation agent, sodium polyacrylate etc. can be mentioned.

  As a residue improving agent, 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 can be mentioned.

  As the developability improver, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono (meth) acrylate etc Can be mentioned.

(Other organic dyes etc.)
The composition may contain known organic dyes other than organic dyes as [A] phthalocyanine compounds and [B] infrared shielding agents as copper compounds. Other organic dyes include diiminium compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quaterylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexaphyrins. Compounds etc. (except those containing a copper atom) can be mentioned. In addition, phthalocyanine compounds other than [A] phthalocyanine compounds and phthalocyanine compounds as [B] infrared shielding agents can also be used.

  In addition, it is preferable to use together [A] phthalocyanine compound and phthalocyanine compounds other than [A] phthalocyanine compound (Hereafter, it is also 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, even more preferably 800 nm, still more preferably 750 nm, and even more preferably 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 even more preferably 50 nm. On the other hand, the upper limit of this difference is preferably 100 nm, more preferably 80 nm, and even more preferably 50 nm. By using such a phthalocyanine compound in combination, it is possible to further enhance the visible light transmittance and the infrared shielding property of the obtained optical filter. Moreover, the visible light uniform transmittance of the obtained optical filter can also be improved. The [a] phthalocyanine compound also includes a phthalocyanine compound as a copper compound which is a [B] infrared shielding agent. Examples of the [a] phthalocyanine compound include various conventionally known phthalocyanine compounds.

  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 even more preferably 80% by mass, and 90% by mass is more It may be preferable, and 99 mass% may be more preferable. It may be preferable to substantially contain only the [A] phthalocyanine compound as the organic dye. The composition can improve productivity by thus reducing the content of other organic dyes. Moreover, it is also possible to enhance the visible light uniform transmission in the obtained optical filter.

  In addition, the number of types of organic dyes contained in the composition, including the [A] phthalocyanine compound, is preferably 3 or less, more preferably 2 or less, and sometimes 1 or more. By reducing the number of types of organic dyes contained in this manner, it is possible to enhance productivity and to enhance the uniform visible light transmittance of the obtained optical filter. When two or more organic dyes are used, it is preferable to use the [A] phthalocyanine compound in combination with a phthalocyanine compound other than the [A] phthalocyanine compound.

(solvent)
The composition is usually prepared as a liquid composition containing a solvent (dispersion medium). As a solvent, as long as it disperse | distributes or melt | dissolves the other component, and does not react with these components and it has moderate volatility, it can select suitably and can be used.

As such 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, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as 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 ,
Alkyl 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, cyclohexanol, etc.
Keto alcohols such as diacetone alcohol,
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, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate,
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like
Linear ketones such as methyl ethyl ketone, 2-heptanone and 3-heptanone, and ketones such as cyclic ketones such as cyclopentanone and cyclohexanone,
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate,
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate ,
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, butyrate i -Other esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc.
Aromatic hydrocarbons such as toluene and xylene,
Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can be mentioned.

  The content of the solvent in the composition is not particularly limited. As a minimum of solid content concentration (total concentration of each ingredient except a solvent) in the composition concerned, 5 mass% is preferred and 10 mass% is more preferred. On the other hand, as a maximum of this solid content concentration, 50 mass% is preferred and 40 mass% is more preferred. By setting the solid content concentration in the above range, the 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 a metal oxide as a [B] infrared shielding agent, and a [C] dispersant, first, a dispersion containing a [B] infrared shielding agent, a [C] dispersant and a solvent A liquid may be prepared, and the [A] phthalocyanine compound and other components may be added to this dispersion and mixed. The dispersion or the composition may be subjected to filtration treatment as necessary to remove aggregates.

<Infrared 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 excellent visible light transmittance and infrared shielding property even when the type of the organic dye contained is small. Moreover, the said infrared rays shielding film (I) is excellent in the uniform transmittance | permeability in a visible light area | region.

  It is preferable that the said infrared rays shielding film (I) is what is integrated in a solid-state image sensor as one structural member. In this case, the infrared shielding film (I) alone functions as an optical filter (infrared cut filter). By incorporating the infrared shielding film (I) into a 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) may be, for example, an outer surface side of a microlens of the solid-state imaging device, between a microlens and a color filter, and a color filter It can be disposed between the photodiode and the like. The infrared shielding film (I) is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

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

  The solid-state imaging device provided with the above optical filter is useful for digital still cameras, cameras for mobile phones, digital video cameras, PC cameras, surveillance cameras, cameras for automobiles, portable information terminals, personal computers, video games, medical devices and the like.

  The infrared shielding film (I) can be formed, for example, by the following method. First, the composition is applied onto a support, and then prebaked to evaporate the solvent to form a coating. Then, the coating film is exposed and developed using a developer to dissolve and remove the non-exposed part of the coating film. Thereafter, by post-baking, an infrared shielding film (I) patterned in a predetermined shape is obtained. When the composition does not contain the [D] polymerizable compound and the [E] polymerization initiator, curing treatment such as exposure may not be performed. Further, the development process may not be performed, and in this case, the infrared ray shielding film (I) which is not patterned can be formed.

  The above-mentioned transparent substrate, a micro lens, a color filter etc. correspond as said support body which apply | coats the said composition. The application may be carried out by any suitable application 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), a bar coating method and the like.

  The heat drying conditions in the pre-baking are, for example, 70 ° C. or more and 110 ° C. or less, and about 1 minute or more and 10 minutes or less.

As a light source of radiation used for exposure of a coating film, for example, a lamp light source such as xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, argon ion laser, YAG laser, Laser light sources such as XeCl excimer laser and nitrogen laser can be mentioned. An ultraviolet LED can also be used as an exposure light source. The wavelength is preferably radiation in the range of 190 nm to 450 nm. Exposure of radiation, typically on the order 10J / ^{m 2} or more 50,000J / ^{m 2} or less.

  An alkaline developer is generally used as the developer. Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkali developer. After development, usually, washing is performed.

  As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method or the like can be applied. The developing conditions are about 5 seconds to 300 seconds at normal temperature.

  The post-baking conditions are usually 180 ° C. or more and 280 ° C. or less, and 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, the upper limit of the average film thickness is usually 5 μm, preferably 3 μm. When the average film thickness of the infrared shielding film (I) is in the above-mentioned range, the balance between the visible light transmittance and the infrared shielding property becomes better. Moreover, the suitable visible light transmittance | permeability and infrared rays transmittance of infrared shielding film (I) can apply the range of infrared shielding film (II) mentioned later.

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

  The optical filter for a solid-state imaging device provided with the infrared shielding film (II) has both excellent visible light transmittance and infrared shielding property. In addition, since the infrared shielding film (II) contains only one or two organic dyes substantially, it is easy to prepare and has high productivity. Here, "containing substantially only one or two organic dyes" means that the content ratio of one or two organic dyes in the total organic dyes contained is 90% by mass or more. It says that there is. It is preferable that this content rate is 99 mass% or more, and it is more preferable that it is 99.9 mass% or more. The infrared shielding film (II) preferably contains substantially only one type of organic dye.

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

  (A) The lower limit of the average value of the transmittance in the wavelength range of 430 nm to 580 nm is 75%, preferably 78%, and more preferably 80%. When the average value of the transmittance is equal to or more than the above 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 wavelength range of 700 nm to 900 nm is 16.5%, but 16% is preferable, 15.5% is more preferable, 15% is more preferable, and 14% is more preferable Sometimes. By the average value of this transmittance | permeability being below the said upper limit, the favorable shielding property of near infrared rays can be exhibited. On the other hand, the lower limit of this average value may be, for example, 5%, 10%, or 12%.

  5. The lower limit of the ratio (S / N ratio) of the average value (S) of transmittance in the range of 430 nm to 580 nm with respect to the average value (N) of transmittance in the range of 700 nm to 900 nm is preferably 5; 2 is more preferable. On the other hand, the upper limit of this ratio may be 10, 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%. Favorable infrared shielding can be exhibited because this transmittance | permeability is below the said upper limit. On the other hand, the lower limit of the transmittance may be, for example, 3%, 5%, or 5.5%.

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

Visible light uniform transmittance = {(average value of transmittance in a wavelength range of 430 nm to 580 nm-minimum value of transmittance in a wavelength range of 430 nm to 580 nm) / average value of transmittance in a wavelength range of 430 nm to 580 nm } × 100 (%)

  The said infrared rays shielding film (II) can be formed, for example by the composition for solid-state image sensors which is one Embodiment of this invention mentioned above. The method of forming the infrared shielding film (II) is also the same as the method described above as the method of forming the infrared shielding film (I). However, the composition to be used substantially contains only one or two organic dyes, and at least the [A] phthalocyanine compound corresponds to the organic dyes. That is, in the infrared shielding film (II), the organic dye is preferably a phthalocyanine compound ([A] phthalocyanine compound) represented by the above formula (1).

  The preferred embodiment of the composition for solid-state imaging device for forming the infrared shielding film (II) is also the same as the composition for solid-state imaging device described above. That is, the infrared shielding film (II) preferably further contains an infrared shielding agent ([B] infrared shielding agent) which is a metal oxide, a copper compound or a combination thereof. Moreover, it is preferable that the [B] infrared shielding agent is cesium-tungsten oxide. The other preferable form of the said infrared shielding film (II) is also the same as that of the infrared shielding film (I) formed from the said composition for solid-state image sensors.

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

<Solid-state imaging device>
The solid-state imaging device according to an embodiment of the present invention is a solid-state imaging device having the infrared ray shielding film (I) or the infrared ray shielding film (II). Since the solid-state imaging device has an infrared shielding film having both excellent visible light transparency and infrared shielding properties even when the type of the organic dye contained is small, good visibility correction is made.

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

  In the solid-state imaging device, the infrared shielding film (I) or the infrared shielding film (II) is an outer surface side of the microlens, between the microlens and the color filter, the color filter, and the plurality of photodiodes. May be provided between the layer to be placed, etc. 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. In addition, even if another layer (planarization layer etc.) is provided between the infrared ray shielding film (I) or the infrared ray shielding film (II) and a micro lens, a color filter, a photodiode etc. Good.

  As a specific example of the said solid-state image sensor, CCD as a camera module, CMOS, etc. are mentioned. The solid-state imaging device is useful for digital still cameras, cameras for mobile phones, digital video cameras, PC cameras, surveillance cameras, cameras for automobiles, portable information terminals, personal computers, video games, medical devices, and the like.

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

Synthesis Example 1
Along the above-mentioned 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. Lithium pentoxide (solid lithium and pentan-1-ol) was used as “1. base”, and glacial acetic acid was used as “2. acid”. In addition, vanadyl salt was used as a salt giving M ²⁺ .

Synthesis Example 2
The phthalocyanine compound (a-1) (maximum absorption wavelength 692 nm) represented by a following formula was synthesize | combined using the method as described in stage-of Unexamined-Japanese-Patent No. 05-25177 (Example 1).

Synthesis Example 3
The phthalocyanine compound (a-2) (maximum absorption wavelength 728 nm) represented by a following formula was synthesize | combined using the method as described in stage of Unexamined-Japanese-Patent No. 2016-204536 (Example 4).

The other dyes used are as follows.
Compound (a-3): “FDN-002” (Phthalocyanine compound: maximum absorption wavelength 807 nm) of Yamada Chemical Industry Co., Ltd.

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.

[Preparation 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 mg KOH / g) as a dispersing agent, and as a solvent (dispersion medium) 61.89 parts by mass of cyclopentanone (CPN) was prepared. These were filled in a container together with 2000 parts by mass of 0.1 mm diameter zirconia beads and dispersed by a paint shaker to obtain a dispersion having an average particle diameter (D50) of 19 nm. In addition, average particle diameter was measured by DLS method using the light-scattering measurement apparatus ("ALV-5000" of ALV company in Germany).

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

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

[Evaluation]
The following evaluation was performed using each obtained composition. The evaluation results are shown in Table 1.

Each composition was apply | coated by the spin coat method so that it might become a predetermined | prescribed film thickness on a glass substrate. Thereafter, the coated film was heated at 100 ° C. for 120 seconds, and exposed to an intensity of 1000 mJ / cm ² with an i-line stepper. Subsequently, the infrared shielding film with an average film thickness of 1.4-1.6 micrometers was produced on the glass substrate by heating at 220 degreeC for 300 second. Each average film thickness is shown in Table 1. In addition, the film thickness was measured by a stylus type step difference meter ("Alpha step IQ" by Yamato Scientific Co., Ltd.). Next, the transmittance | permeability in each wavelength area of the infrared shielding film produced on the said glass substrate was measured in comparison with a glass substrate using the spectrophotometer ("V-7300" of JASCO Corporation). From the obtained spectrum, evaluation was performed according to the following evaluation criteria. The transmission spectrum of the infrared shielding film of Example 1 is shown in FIG. In the transmission spectrum of FIG. 1, the horizontal axis is wavelength (nm) and the vertical axis is transmittance (%).

(Visible light transmission)
The average transmittance at 430-580 nm was calculated. When the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film is reduced. Moreover, about the said average transmittance | permeability, the following references | standards evaluated.
A: 80% or more B: 70% or more and less than 80% C: less than 70%

(Infrared shielding 1)
The average transmittance of 700-900 nm was calculated. When the average transmittance is 20% or more, the amount of noise increases when used as an infrared shielding film. Moreover, about the said average transmittance | permeability, the following references | standards evaluated.
A: less than 15% B: 15% or more and less than 20% C: 20% or more

(Infrared shielding 2)
About the transmittance | permeability of wavelength 1200nm, it can be said that the transmittance | permeability shows less than 15%, and the practically favorable infrared shielding property is shown. 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)
The ratio (S / N ratio) of the average transmittance (S) in the visible light region (430-580 nm) and the average transmittance (N) in the infrared region (700-900 nm) was taken to estimate practical performance. The higher the S / N ratio, the better the performance, and when it was 5 or more, it was judged that it could be used at a practical level. The following criteria evaluated S / N ratio.
A: 5 or more B: less than 5

(Visible light uniform transparency)
From the average transmittance (S) in the visible light range (430-580 nm) and the minimum transmittance (S _min ) in the visible light range, X (visible light uniform transmittance) is determined based on the following equation Uniform permeability was evaluated.
X = ((S−S _min ) / S) × 100 (%)
It can be judged that the uniform transmittance of visible light is higher as X is smaller. The above X was evaluated according to the following criteria.
A: less than 10% B: 10% or more

  As shown in Table 1 above, in the infrared shielding films of Examples 1 to 3, both the visible light transmittance and the infrared shielding property are good (A or B), and also the uniform transmittance of visible light. Excellent. Moreover, it turns out that the infrared rays shielding film of Examples 1-3 can express such a favorable characteristic, although the kind containing organic dye is only 1 type or 2 types.

  The composition for solid-state imaging device 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.

Claims (14)

The composition for solid-state imaging devices containing the 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 is M 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. Each n is independently an integer of 3 to 6) The composition for solid-state imaging devices according to claim 1, further comprising an infrared shielding agent which is a metal oxide, a copper compound (excluding 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 cesium tungsten oxide.   The composition for a solid-state imaging device according to claim 2 or 3, wherein the content of the metal oxide, the copper compound or the combination thereof is 1% by mass to 70% by mass with respect to the total solid content.   The composition for a solid-state imaging device according to any one of claims 1 to 4, 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 any one of claims 1 to 5, wherein R in the formula (1) is a linear or branched alkyl group having 1 to 12 carbon atoms. The M in the above formula (1) is H ₂ , Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO or TiO. The composition for solid-state image sensors of any one of these.   The infrared shielding film for solid-state image sensors formed from the composition for solid-state image sensors of any one of Claims 1-7. An infrared shielding film for a solid-state imaging device substantially containing only one or two organic dyes and satisfying the following (A) to (C).
(A) The average value of the transmittance in the range of 430 nm to 580 nm is 75% or more (B) The average value of the transmittance in the range of 700 nm to 900 nm is 16.5% or less (C) The transmittance at 1200 nm Less than 10% (D) The infrared shielding film according to claim 9, wherein the visible light uniform transmittance represented by the following formula is 10% or less.
Visible light uniform transmittance = {(average value of transmittance in a wavelength range of 430 nm to 580 nm-minimum value of transmittance in a wavelength range of 430 nm to 580 nm) / average value of transmittance in a wavelength range of 430 nm to 580 nm } × 100 (%) The infrared rays shielding film of Claim 9 or 10 which further contains the infrared rays shielding agent which is a metal oxide, a copper compound, or these combination.   The infrared shielding film according to claim 11, wherein the infrared shielding agent is cesium tungsten oxide. The infrared shielding film according to any one of claims 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'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. M may be bonded to each other to form an aromatic ring together with the carbon chain to which they are attached M is two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal derivative. Are each independently an integer of 3 to 6.)   A solid-state imaging device having the infrared shielding film according to any one of claims 8 to 13.

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