TWI746822B - Composition for solid-state imaging device, infrared shielding film, and solid-state imaging device - Google Patents

Abstract

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

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.

Charge-Coupled Device (CCD) image sensors or Complementary Metal Oxide Semiconductor (CMOS) image sensors are installed in video cameras, digital cameras, mobile phones with camera functions, etc. Solid-state imaging element. The sensitivity of the photodiodes included in these solid-state imaging elements spans from the visible light region to the infrared region. Therefore, a solid-state imaging element is provided with a filter to block infrared rays. With the infrared blocking filter, the sensitivity of the solid-state imaging device can be corrected in a manner close to the visual acuity of human beings.

The infrared shielding filter contains a dye or pigment as an infrared shielding agent. The infrared shielding agent is required to fully penetrate visible light and absorb infrared light. As one of the infrared shielding agents, especially a good shielding agent for near-infrared rays, the use of a phthalocyanine compound has been studied (see Japanese Patent Laid-Open No. 2008-201952).

However, compared with the previous infrared blocking filter using phthalocyanine compound Among them, the visible light penetration and infrared shielding properties are not sufficiently satisfied. Therefore, in order to exhibit good characteristics, for example, a plurality of infrared shielding agents may be mixed and used. The use of the various infrared shielding agents has also become the main cause of high cost and reduced productivity. In addition, in the conventional infrared shielding filter using a phthalocyanine compound, there may be a large deviation in the transmittance in the visible light region. In this case, good visual acuity correction has not been carried out either.

[Prior Art Literature]

[Patent Literature]

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

However, in the conventional infrared shielding filter for solid-state imaging devices using a phthalocyanine compound, the visible light transmittance and infrared shielding properties are not sufficiently satisfied. Therefore, in order to exhibit good characteristics, for example, a plurality of infrared shielding agents may be mixed and used. The use of the various infrared shielding agents has also become the main cause of high cost and reduced productivity. In addition, in the conventional infrared shielding filter using a phthalocyanine compound, there may be a large deviation in the transmittance in the visible light region. In this case, good visual acuity correction has not been carried out either.

The present invention is made in view of the foregoing circumstances, and its object is to provide a composition for a solid-state imaging device, an infrared shielding film for a solid-state imaging device, and a solid-state imaging device having the infrared shielding film, and the composition for a solid-state imaging device Even when the types of organic pigments contained are small, it can also form a good Optical filters for solid-state imaging devices with visible light transmittance and infrared shielding properties. The infrared-shielding film for solid-state imaging devices has good visible light penetration even when the types of organic pigments contained are small And infrared shielding.

The invention completed in order to solve the above-mentioned problem is a composition for a solid-state imaging device containing a phthalocyanine compound represented by the following formula (1) (hereinafter, also referred to as "[A] phthalocyanine compound").

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

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

Yet another invention completed in order to solve the problem is an infrared shielding film (II) for a solid-state imaging element, which substantially contains only one or two organic dyes, and satisfies the following (A) to (C).

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

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

(C) The transmittance at a wavelength of 1200nm is less than 10%

Yet another invention completed in order to solve the above-mentioned problem is a solid-state imaging device having the infrared ray shielding film (I) or the infrared ray shielding film (II).

According to the present invention, it is possible to provide a composition for a solid-state imaging device, an infrared shielding film for a solid-state imaging device, and a solid-state imaging device having the infrared shielding film. When there are few types, it is possible to form an optical filter for solid-state imaging devices that has both good visible light transmittance and infrared shielding properties. The infrared-shielding film for solid-state imaging devices can also be formed even when the types of organic pigments contained are small. In the case of, it also has good visible light penetration and infrared shielding.

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

Hereinafter, the 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 a solid-state imaging element according to an embodiment of the present invention (hereinafter, also simply referred to as "composition") contains [A] a phthalocyanine compound. The composition preferably further contains [B] an infrared shielding agent, and the [B] infrared shielding agent is a metal oxide, a copper compound (except for the [A] phthalocyanine compound), or a combination of these.

([A] Phthalocyanine compound)

[A] The phthalocyanine compound is a compound represented by the following formula (1). [A] The phthalocyanine compound has high transmittance in the visible light region (for example, a wavelength range of 430 nm or more and 580 nm or less), and on the other hand, it has high shielding properties in the near infrared region (for example, a wavelength region of 700 nm or more and 900 nm or less). This composition contains the above-mentioned [A] phthalocyanine compound, and therefore, even when the types of organic dyes contained are small, it is possible to form an optical filter having both good visible light transmittance and infrared shielding properties. In addition, since this composition contains the [A] phthalocyanine compound, it can form an optical filter with high uniform transmittance in the visible light region.

[化2]

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

Examples of the alkyl group represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tertiary butyl, etc. A straight-chain or branched alkyl group with 1 to 30 carbon atoms.

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

As said R, an alkyl group is preferable, and a C1-C12 linear or branched alkyl group is more preferable. Furthermore, the upper limit of the carbon number of the alkyl group is preferably 6, more preferably 4, more preferably 2. As said R, methyl is particularly preferred.

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

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

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

The X is preferably a hydrogen atom.

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. Furthermore, the so-called divalent metal atom refers to a metal atom that can become a divalent cation.

Here, the derivative of a metal atom refers to an atom group containing a metal atom. The so-called trivalent metal atom refers to a metal atom that can become a trivalent cation. Examples of trivalent metal atoms include Al, In, and the like. The tetravalent metal atom refers to a metal atom that can become a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, Sn, and the like. Furthermore, metal atoms also include semi-metal atoms. Examples of derivatives of trivalent or tetravalent metal atoms 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.

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

The lower limit of n is preferably 4. As the upper limit of 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 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 within the above range, an optical filter having both better visible light transmittance and infrared 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 the following scheme (scheme) 1.

[化3]

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

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

The lower limit of the content of [A] the 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, 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. By setting the content of the [A] phthalocyanine compound within the above-mentioned range, the visible light transmittance and infrared shielding properties of the obtained optical filter achieve a better balance.

[A] The phthalocyanine compound may be used individually by 1 type, and may mix and use 2 or more types. Among them, it is preferable to use only one or two [A] phthalocyanine compounds, and it is more preferable to use only one [A] phthalocyanine compound. [A] Only one phthalocyanine compound can exhibit good visible light transmittance and infrared shielding properties. Therefore, by reducing the number of [A] phthalocyanine compounds used, good visible light transmittance and infrared shielding properties can be exhibited, and productivity can be improved.

([B] Infrared shielding agent)

[B] The infrared shielding agent is a metal oxide, a copper compound ([A] phthalocyanine compound is excluded), or a combination of these. [B] The infrared shielding agent is preferably a compound having a maximum absorption wavelength in the range of 800 nm or more and 2000 nm or less. By combining the [B] infrared shielding agent and [A] phthalocyanine compound, the resulting optical filter The infrared shielding performance is further improved.

[B] Metal oxides as infrared shielding agents include, for example, tungsten oxide compounds, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), and titanium dioxide (TiO 2 ). ₂ ), zirconia (ZrO ₂ ), spinel (MgAl ₂ O ₄ ), etc.

[B] Copper compounds as infrared shielding agents include copper phthalocyanine-based compounds and other copper complex compounds. Examples of copper phthalocyanine-based compounds include copper phthalocyanine, copper phthalocyanine chloride, copper phthalocyanine bromide chloride, copper phthalocyanine bromide, and the like.

[B] The infrared shielding agent is preferably a metal oxide, and more preferably a tungsten oxide compound. The tungsten oxide-based compound is an infrared shielding agent that has high absorption of ultraviolet rays (especially infrared rays with a wavelength of about 800 nm or more and 1200 nm or less) (that is, high infrared shielding properties) and low absorption of visible light. Therefore, when the composition contains a tungsten oxide-based compound, the obtained optical filter can maintain good visible light transmittance and improve infrared shielding properties. [B] One kind of infrared shielding agent may be used alone, or two or more kinds may be used in combination.

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

A _x WO _y . . . (2)

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

The metal element represented by A in the formula (2) includes: 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, etc. The metal element represented by A may be one type or two or more types.

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. The lower limit of x is preferably 0.01, more preferably 0.1. On the other hand, when x is 1.1 or less, it is possible to more reliably avoid the generation of impurity phases in the tungsten oxide-based compound. The upper limit of x is preferably 1, more preferably 0.5.

When y in the formula (2) is 2.2 or more, the chemical stability of the 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 formula (2) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, etc., preferably Cs _0.33 WO ₃ and Rb _0.33 WO ₃ , more preferably Cs _0.33 WO ₃ .

[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 below the upper limit, the visible light transmittance can be further improved. On the other hand, for reasons such as ease of handling at the time of manufacture, the average particle diameter of [B] the infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

[B] The infrared shielding agent can also be synthesized by a known method, and can be obtained as a commercially available product. 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. In addition, the tungsten oxide-based compound can also be obtained as a dispersion of tungsten fine particles such as "YMF-02" of Sumitomo Metal Mining Co., Ltd., for example.

[B] The lower limit of the content of the 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. The lower limit of the content is more preferably 20% by mass, and more preferably 30% by mass. On the other hand, as the upper limit of the content, it is preferably 70% by mass, more preferably 65% by mass, and still more preferably 60% by mass. By setting the content of the infrared shielding agent [B] within the above-mentioned range, the visible light transmittance and infrared shielding properties of the obtained optical filter achieve a better balance.

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

([C] Dispersant)

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

[C] Dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, Polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester dispersant, (meth)acrylic dispersant, etc. Among these, a (meth)acrylic dispersant is preferable. [C] The dispersant is preferably a block copolymer.

[C] Dispersants are commercially available. For example, (meth)acrylic dispersants can include Disperbyk-2000, Disperbyk-2001, BYK- LPN6919, BYK-LPN21116, BYK-LPN22102 (the above are manufactured by BYK), urethane-based dispersants can include Disperbyk-161 , Disperbyk -162, Disperbyk -165, Disperbyk -167, Disperbyk -170, Disperbyk -170 (Disperbyk) 182, Disperbyk-2164 (the above is made by BYK), Solsperse 76500 (made by Lubrizol (stock)), Examples of polyethyleneimine-based dispersants include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and examples of polyester-based dispersants include Ajisper PB821 and Ajisper. (Ajisper) PB822, Ajisper (Ajisper) PB880, Ajisper (Ajisper) PB881 (the above are manufactured by Ajinomoto Fine-Techno Co., Ltd.), in addition to the BYK ( BYK)-LPN21324 (manufactured by BYK) and the like.

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

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

([D] polymerizable compound)

The composition preferably further contains [D] a polymerizable compound. When the composition contains [D] a polymerizable compound, good curability or good heat resistance of the obtained optical filter can be exhibited. [D] The polymerizable compound refers to a compound having two or more polymerizable groups. As the polymerizable group, for example, an ethylenically unsaturated group, an oxirane group, an oxetanyl group, an N-alkoxymethylamino group, etc. may be mentioned. [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 more preferably two or more N-alkoxymethylamino groups The (meth)acrylic compound. [D] The polymerizable compound can be used singly or in combination of two or more.

As a compound having two or more (meth)acryloyl groups, it can be listed Examples include: polyfunctional (meth)acrylates as reactants of aliphatic polyhydroxy compounds and (meth)acrylic acid, polyfunctional (meth)acrylates modified with caprolactone, and modified with alkylene oxide Polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates such as the reactants of (meth)acrylates with hydroxyl groups and polyfunctional isocyanates, and (meth)acrylates with hydroxyl groups (meth) ) Polyfunctional (meth)acrylates having carboxyl groups such as reactants of acrylates and acid anhydrides.

Here, as the aliphatic polyhydroxy compound, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, or glycerin, trimethylolpropane, pentaerythritol, dihydric Aliphatic polyhydroxy compounds with trivalent or higher valence such as pentaerythritol. As the (meth)acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, two Pentaerythritol penta(meth)acrylate, glycerol dimethacrylate, etc. As said polyfunctional isocyanate, toluene 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, or pyromellitic dianhydride, Tetrabasic acid dianhydrides such as biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

As specific examples of the compound having two or more (meth)acryloyl groups, for example, ω-carboxy polycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, 1, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Ester, polypropylene glycol di(meth)acrylate, bisphenoxyethanol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, 2-hydroxy-3-(meth)acrylate Base) acryloxy propyl methacrylate, 2-(2'-vinyloxyethoxy) ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( Meth) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl) Phosphoric acid ester, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, urethane (meth)acrylate compound, etc.

Among the compounds having two or more (meth)acryloyl groups, a polyfunctional (meth)acrylate is preferred, and a polyfunctional one having 3 or more and 10 (meth)acryloyl groups is more preferred (Meth)acrylate. 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)acetylene carbamide, etc.

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

([E] polymerization initiator)

The composition preferably contains [E] a polymerization initiator. [E] The polymerization initiator includes a photopolymerization initiator, a thermal polymerization initiator, and the like, and a photopolymerization initiator is preferred. Thereby, photosensitivity (radiation sensitivity) can be imparted to the composition. The term "photopolymerization initiator" refers to a compound that generates active species that initiate polymerization of the [D] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, extreme ultraviolet light, electron beam, or X-ray. [E] One type of polymerization initiator can be used, or two or more types can be used in combination.

[E] The polymerization initiator includes, for example, thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-oxime-based compounds, onium salt-based compounds, and benzoin-based compounds. Compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, imine sulfonate-based compounds, etc. 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 thioxanthone compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4 -Dichlorothioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2,4-Diisopropylthioxanthone, etc.

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

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

Furthermore, in the case of using a biimidazole-based compound, it is preferable to use a hydrogen donor in combination in terms of improving sensitivity. The "hydrogen donor" as used herein refers to a compound that can donate hydrogen atoms to radicals generated from a biimidazole-based compound by exposure to light. Examples of hydrogen donors include thiol-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis(dimethylamino)benzophenone, 4, Amine-based hydrogen donors such as 4'-bis(diethylamino)benzophenone.

As the triazine compound, for example, the compounds described in paragraphs [0063] to paragraph [0065] of Japanese Patent Publication No. 57-6096 and Japanese Patent Application Publication No. 2003-238898 can be cited.

Examples of O-acetoxime compounds include: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzyloxime), ethyl ketone-1 -[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethyl ketone-1-[9-ethyl Base-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethyl ketone-1-[ 9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzyl}-9H-carbazole-3 -Radical]-1-(O-acetyloxime) and the like. As commercially available products of O-acetoxime-based compounds, NCI-831, NCI-930 (the above are manufactured by ADEKA Co., Ltd.), OXE-03, OXE-04 (the above are BASF ( BASF) manufactured by the company) and so on.

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

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

(Binder resin)

The composition may further contain a binder resin. The binder resin is not particularly limited, but a resin having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group is preferred. Among them, a polymer having a carboxyl group (hereinafter, also referred to as a "carboxyl group-containing polymer") is preferred. Examples of carboxyl group-containing polymers include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomers (1)") and other copolymerizable ethylenically unsaturated monomers. A copolymer of a weight body (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] ester, ω -Carboxyl polycaprolactone mono(meth)acrylate, p-vinyl benzoic acid, etc.

Examples of the unsaturated monomer (2) include N-substituted maleimines such as N-phenylmaleimines, N-cyclohexylmaleimines, styrene, and α -Methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthene and other aromatic vinyl compounds, methyl (meth)acrylate, (methyl) N-Butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol ( Polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol (polymerization degree 2-10) mono(meth)acrylic acid Ester, polypropylene glycol (degree of polymerization 2~10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane- 8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide of p-cumylphenol Modified (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloxymethyl]oxy Etidine, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and other (meth)acrylates, cyclohexyl vinyl ether, isobornyl vinyl ether, Tricyclic [5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, etc. Vinyl ether, polystyrene, polymethyl(meth)acrylate, poly(n-butyl)acrylate, polysiloxane are equal to a giant monomer with a single (meth)acrylic acid group at the end of the polymer molecular chain Body etc.

In addition, as a binder resin, it can also be used for side chains with (meth)acrylic acid A carboxyl group-containing polymer with a polymerizable unsaturated bond such as an alkenyl group. In addition, polysiloxane etc. can also be used as a binder resin.

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

(additive)

The composition may also contain various additives as needed.

Examples of additives include surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, residue improvers, developability improvers, and the like.

As the surfactant, a fluorine surfactant, a silicone surfactant, and the like can be cited. As content of a surfactant, it can be normally 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] phthalocyanine compounds.

Examples of adhesion promoters include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris(2-methoxyethoxy) silane, and N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-condensation Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropane Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

Examples of antioxidants include: 2,2-thiobis(4-methyl-6-tertiary butyl) Phenol), 2,6-di-tert-butylphenol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis[2 -[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetra Oxa-spiro[5.5]undecane, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the like. As content of an antioxidant, normally, 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.

Examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenones, and the like.

As the anti-aggregation agent, sodium polyacrylate and the like can be cited.

Examples of residue improvers 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, etc.

As the developability improver, succinic acid mono[2-(meth)acryloxyethyl] ester, phthalic acid mono[2-(meth)acryloxyethyl] ester, ω -Carboxylic polycaprolactone mono(meth)acrylate and other agents.

(Other organic pigments, etc.)

This composition may contain a well-known organic dye other than the organic dye which is [A] a phthalocyanine compound and the copper compound which is [B] an infrared shielding agent. Examples of other organic pigments include diimine compounds, squaraine ylide compounds, cyanine compounds, naphthalocyanine compounds, quateracene compounds, ammonium compounds, imine compounds, azo compounds, anthraquinone compounds, porphyr Morinoline compounds, pyrrolopyrrole compounds, oxocyanation Compounds, croconium compounds, hexaphyrin compounds, etc. (excluding those containing copper atoms). In addition, phthalocyanine compounds other than [A] a phthalocyanine compound and [B] an infrared shielding agent may also be used.

Furthermore, it is preferable to use the [A] phthalocyanine compound in combination with a phthalocyanine compound other than the [A] phthalocyanine compound (hereinafter, also referred to as "[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, sometimes even more preferably 750 nm, and sometimes 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, sometimes even more preferably 800 nm, sometimes even more preferably 750 nm, and sometimes even more preferably 700nm. The lower limit of the difference between the maximum absorption wavelength of the [A] phthalocyanine compound and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm, and sometimes even more preferably 50 nm. On the other hand, the upper limit of the difference is preferably 100 nm, more preferably 80 nm, and sometimes even more preferably 50 nm. By using the phthalocyanine compound in combination, the visible light transmittance and infrared shielding properties of the obtained optical filter can be further improved. In addition, the uniform transmittance of visible light of the obtained optical filter can also be improved. Furthermore, [a] the phthalocyanine compound also includes a phthalocyanine compound which is a copper compound which is an infrared shielding agent [B]. [a] The phthalocyanine compound includes various conventionally known phthalocyanine compounds.

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

In addition, as the number of types of organic dyes contained in the composition, [A] phthalocyanine compounds are also included, and three or less types are preferable, two or less types are more preferable, and one type is even more preferable in some cases. Even if the number of types of organic dyes contained is reduced in this way, productivity can be improved, and the visible light uniform transmittance of the obtained optical filter can be improved. Furthermore, when two or more organic dyes are used, it is preferable to use [A] a phthalocyanine compound and [A] a phthalocyanine compound other than the phthalocyanine compound in combination.

(Solvent)

This composition is usually prepared as a liquid composition containing a solvent (dispersion medium). As the solvent, any one that disperses or dissolves other components, does not react with these components, and has moderate volatility, can be appropriately selected and used.

Examples of the solvent include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly)alkylene glycol monoalkyl ethers, methyl lactate, ethyl lactate and other alkyl lactates, methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, pungent Alcohol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols, diacetone alcohol and other ketone alcohols, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl 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 and other (poly)alkylene glycol monoalkyl ether acetates, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, tetrahydrofuran and other ethers, methyl ethyl ketone, 2-heptanone, 3-heptanone and other chain ketones, cyclopentanone, cyclohexanone and other cyclic ketones, propylene glycol two Acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate and other diacetate esters, methyl 3-methoxypropionate, 3-methoxypropionic acid Alkoxy carboxylates such as ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate, etc. Esters, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyl N-Propyl Acetate, Isopropyl Butyrate, n-Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, N-Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, 2-oxobutyl Other esters such as ethyl ester, aromatic hydrocarbons such as toluene and xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Amines or internal amides, etc.

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

(Preparation)

The preparation method of the composition is not particularly limited, and it can be prepared by mixing the components. For example, in the case where the composition contains a metal oxide as [B] an infrared shielding agent and a [C] dispersant, the following method can be used: firstly, a preparation containing [B] an infrared shielding agent, [C] a dispersant, and In the dispersion liquid of the solvent, [A] the phthalocyanine compound or other components are added to the dispersion liquid and mixed. The dispersion or the composition may also be filtered as necessary to remove aggregates.

<Infrared shielding film (I)>

The infrared shielding film (I) of one embodiment of the present invention is an infrared shielding film for solid-state imaging devices formed from the composition for solid-state imaging devices. Regarding the optical filter for a solid-state imaging element having this infrared shielding film (I), even when the types of organic dyes contained are small, it has both good visible light transmittance and infrared shielding properties. 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) functions as an optical filter (infrared cut filter) as a single body. Since the infrared shielding film (I) is incorporated into the solid-state imaging device, a large process margin can be obtained, which is preferable. In the case where the infrared shielding film (I) is incorporated into the solid-state imaging device, the infrared shielding film (I) can be arranged on the outer surface side of the microlens of the solid-state imaging device, between the microlens and the color filter, for example. Between the color filter and the photodiode, etc. The infrared shielding film (I) is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

As the optical filter, the infrared shielding film (I) may be layered on the surface of a transparent substrate. As the transparent substrate, glass, transparent resin, or the like can be used. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyimide, and polyimide. The optical filter can also be preferably used as an infrared cut filter in a solid-state imaging device, etc.

The solid-state imaging element equipped with the optical filter is used in digital still cameras, mobile phone cameras, digital video cameras, personal computer (PC) cameras, surveillance cameras, automotive cameras, portable information terminals, computers, Useful in video games, medical equipment, etc.

This infrared shielding film (I) can be formed by the following method, for example. First, after coating the composition on a support, prebaking is performed to evaporate the solvent to form a coating film. Then, after exposing the coating film, development is performed using a developing solution, and the unexposed part of the coating film is dissolved and removed. Afterwards, by post-baking, you can get Patterned into a predetermined shape infrared shielding film (I). In addition, when the composition does not contain [D] polymerizable compound and [E] polymerization initiator, hardening treatment such as exposure may not be performed. In addition, the development process may not be performed, and in this case, an unpatterned infrared shielding film (I) can be formed.

As the support on which the composition is applied, the transparent substrate, microlens, color filter, etc. are suitable. Suitable coating methods such as spray method, roll coating method, spin coating method (spin coating method), slot die coating method (slit coating method), bar coating method, etc. can be used for the coating.

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

As the light source of the radiation used in the exposure of the coating film, for example, a light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc., or an argon ion laser , Yttrium aluminum garnet (YAG) laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the exposure light source, an ultraviolet light emitting diode (LED) can also be used. The wavelength is preferably radiation within a range of 190 nm or more and 450 nm or less. The radiation exposure is generally 10J / m ² or more and 50,000J / or less about ² m.

As the developer, an alkaline developer is usually used. As the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]- Aqueous solutions of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. In the alkaline developer, for example, suitable The amount of methanol, ethanol and other water-soluble organic solvents or surfactants. In addition, water washing is usually performed after development.

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

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

As the lower limit of the average film thickness of the infrared shielding film (I) formed in the above-mentioned manner, it is usually 0.5 μm, preferably 1 μm. On the other hand, as the upper limit of the average film thickness, it is usually 5 μm, preferably 3 μm. When the average film thickness of the infrared shielding film (I) is within the above range, the balance between visible light transmittance and infrared shielding properties becomes better. In addition, the preferable visible light transmittance and infrared transmittance of the infrared shielding film (I) can be applied to the range of the infrared shielding film (II) described later.

<Infrared shielding film (II)>

The infrared shielding film (II) of one embodiment of the present invention is an infrared shielding film for solid-state imaging devices, which substantially contains only one or two organic dyes, and satisfies the following (A) to (C).

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

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

(C) The transmittance at a wavelength of 1200nm is less than 10%

The optical filter for a solid-state imaging element provided with this infrared shielding film (II) has both good visible light transmittance and infrared shielding properties. In addition, the infrared shielding film (II) substantially contains only one or two organic dyes, so it is easy to prepare and has high productivity. Here, "substantially containing only one or two organic dyes" means that the content of one or two organic dyes in all organic dyes contained is 90% by mass or more. The content ratio is preferably 99% by mass or more, more preferably 99.9% by mass or more. The infrared shielding film (II) preferably contains substantially only one organic pigment.

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).

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

(B) The upper limit of the average value of the transmittance in the 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 sometimes even more preferably 14. %. When the average value of the transmittance is equal to or less than the upper limit, good shielding properties of near-infrared rays can be exhibited. On the other hand, as the lower limit of the average value, for example, it may be 5%, may be 10%, or may be 12%.

As the average value (S) of the transmittance in the range of wavelength 430nm or more and 580nm or less relative to the wavelength in the range of 700nm or more and 900nm or less The lower limit of the ratio (S/N ratio) of the average value (N) of the transmittance is preferably 5, more preferably 5.2. On the other hand, the upper limit of the 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%. When the transmittance is equal to or lower than the upper limit, good infrared shielding properties can be exhibited. On the other hand, as the lower limit of the transmittance, for example, it may be 3%, may be 5%, or may be 5.5%.

In this infrared shielding film (II), it is preferable that the following (D) is satisfied.

(D) The uniform transmittance of visible light expressed by the following formula is 10% or less

The upper limit of the uniform transmittance of visible light is more preferably 9%, and still more preferably 8%. When the uniform transmittance of visible light is less than the upper limit, the transmittance of visible light can be made uniform, and better visual acuity correction can be performed. Furthermore, the lower limit of the uniform transmittance of visible light is not particularly limited, and it may be, for example, 1%, 3%, or 5%.

Visible light uniform transmittance=((average value of transmittance in the range of wavelength 430nm or more and 580nm or less-the lowest value of transmittance in the range of wavelength 430nm or more and 580nm or less)/wavelength of 430nm or more and 580nm or less The average penetration rate in the range)×100(%)

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

A preferable form of the composition for a solid-state imaging device for forming the infrared shielding film (II) is also as described in the composition for a solid-state imaging device. That is, the infrared shielding film (II) preferably further contains an infrared shielding agent ([B] infrared shielding agent), and the infrared shielding agent is a metal oxide, a copper compound, or a combination of these. In addition, [B] the infrared shielding agent is preferably cesium tungsten oxide. Other preferable forms of the infrared shielding film (II) are the same as those of the infrared shielding film (I) formed from the composition for solid-state imaging devices.

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

<Solid-state imaging device>

The solid-state imaging device of one embodiment of the present invention has the infrared shielding film (I) or the solid-state imaging element of the infrared shielding film (II). Regarding this solid-state imaging element, even when the types of organic dyes contained are small, it has an infrared shielding film that has both good visible light transmittance and infrared shielding properties, and therefore good visual acuity correction is performed.

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

In the solid-state imaging element, 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, and Between the color filter and the layer in which a plurality of photodiodes are arranged, 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. Furthermore, other layers (planarization layers, etc.) may be further provided between the infrared shielding film (I) or the infrared shielding film (II) and the microlenses, color filters, photodiodes, and the like.

As a specific example of this solid-state imaging element, CCD, CMOS, etc. which are a camera module are mentioned. The solid-state imaging element is useful in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, portable information terminals, 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>

The phthalocyanine compound (A-1) represented by the following formula (maximum absorption wavelength 735 nm) was synthesized according to the above-mentioned scheme 1. As a starting material, 1,2-dicyano-3,6-bis(4-methoxybutyl)benzene was used. As "1. base", lithium pentanoxide (solid lithium and pentane-1-ol) was used, and as "2. acid", glacial acetic acid was used. In addition, as ^{the salt that provides M 2+} , vanadyl salt is used.

<Synthesis example 2>

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

<Synthesis Example 3>

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

In addition, the dyes used are as follows.

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

<Synthesis Example 4>

The method described in paragraph [0113] of Japanese Patent No. 4096205 was used to synthesize cesium tungsten oxide (Cs _0.33 WO ₃ ) powder.

[Preparation example]

Prepare 25.00 parts by mass of the cesium tungsten oxide, and "BYK-LPM6919" of BYK-Chemie as a dispersant (solid content 61% by mass, amine value 120mgKOH/g) 13.11 parts by mass , And 61.89 parts by mass of cyclopentanone (CPN) as a solvent (dispersion medium). These were filled in a container with 2000 parts by mass of zirconia particles having a diameter of 0.1 mm, and dispersed by a paint shaker, thereby obtaining a dispersion liquid having an average particle diameter (D50) of 19 nm. In addition, the average particle size was measured by a light scattering measuring device ("ALV-5000" of ALV Company, Germany) and a dynamic light scattering (DLS) method.

[Example 1]

In a container, weigh 50.00 parts by mass of the dispersion, 0.75 parts by mass of the phthalocyanine compound (A-1), and "KAYARAD DPHA" (dipentaerythritol hexaacrylic acid) produced by Nippon Kayaku Co., Ltd. as a polymerizable compound. A mixture of ester and dipentaerythritol pentaacrylate) 7.01 parts by mass, ADEKA as a polymerization initiator 0.70 parts by mass of the company's "NCI-930" (O-acetyl oxime compound), 0.02 parts by mass of "FTX-218D" (fluorine-based surfactant) of NEOS as a surfactant, 0.01 parts by mass of "Irganox 1010" (phenolic antioxidant) of BASF as an antioxidant and 41.50 parts by mass of cyclopentanone (CPN) as a solvent were mixed with a mixer. Using a 0.5 μm polytetrafluoroethylene (PTFE) filter, 200 mL of the mixture was subjected to pressure filtration at 0.5 MPa for 3 minutes, thereby obtaining the composition of Example 1.

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

Except having made the composition of each component as shown in Table 1, it carried out similarly to Example 1, and obtained each composition of Example 2-Example 3 and Comparative Example 1-Comparative Example 3.

[Evaluation]

Using each obtained composition, the following evaluation was performed. The evaluation results are shown in Table 1.

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

(Visible light penetration)

Calculate the average transmittance of 430nm-580nm. 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 using the following criteria.

A: More than 80%

B: More than 70% and less than 80%

C: Less than 70%

(Infrared shielding 1)

Calculate the average transmittance of 700nm-900nm. 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 using the following criteria.

A: Less than 15%

B: 15% or more and less than 20%

C: more than 20%

(Infrared shielding 2)

Regarding the transmittance at a wavelength of 1200 nm, it can be said that the transmittance is less than 15% and it shows practically good infrared shielding properties. The transmittance at a wavelength of 1200 nm was evaluated using the following criteria.

A: Less than 10%

B: More than 10% 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 (430nm-580nm) to the average transmittance (N) in the infrared region (700nm-900nm) is obtained, and the practical performance is estimated. The higher the value of the S/N ratio, the better the performance. If it is 5 or more, it is judged to be a practical level and can be used. The S/N ratio was evaluated using the following criteria.

A: 5 or more

B: less than 5

(Visible light uniform penetration)

According to the average transmittance (S) of the visible light region (430nm-580nm) and the lowest transmittance (S _min ) of the visible light region, based on the following formula, X (uniform visible light transmittance) is calculated and evaluated Uniform penetration of visible light.

X=((SS _min )/S)×100(%)

It can be judged that the smaller the X, the higher the uniform penetration of visible light. Regarding the X, the following criteria were used for evaluation.

A: Less than 10%

B: 10% or more

As shown in Table 1, the infrared shielding of Examples 1 to 3 The visible light penetration and infrared shielding properties of the film are both good (A or B), and the uniform penetration of visible light is also excellent. In addition, with regard to the infrared shielding films of Examples 1 to 3, it can be seen that although the organic dye contains only one or two types, the above-mentioned good characteristics can be expressed.

[Industrial availability]

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

Claims (13)

A composition for a solid-state imaging element, which contains a phthalocyanine compound represented by the following formula (1);

In formula (1), multiple Rs are each independently an alkyl group or an aryl group; multiple Xs are each independently a hydrogen atom, a halogen atom or an alkyl group; multiple Xs may also be bonded to each other and to these groups The carbon chains of together form an aromatic ring; M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom; multiple n are each independently an integer of 3-6. The composition for a solid-state imaging device according to the first item of the scope of patent application, which further contains an infrared shielding agent, and the infrared shielding agent is a metal oxide or copper other than the phthalocyanine compound Compound or combination of these. The composition for a solid-state imaging element according to claim 2, wherein the infrared shielding agent is cesium tungsten oxide. The composition for a solid-state imaging device according to the second or third item of the scope of patent application, wherein the content of the metal oxide, copper compound, or combination thereof is 1% by mass or more and 70% with respect to the total solid content. Less than mass%. The composition for a solid-state imaging element according to the scope of patent application item 2 or item 3, 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 the second or third item of the scope of patent application, 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 element as described in item 2 or item 3 of the scope of patent application, wherein M in the formula (1) is H ₂ , Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn , Sn, In, SnCl ₂ , AlCl, VO or TiO. An infrared shielding film for a solid-state imaging element is formed of the composition for a solid-state imaging element as described in any one of items 1 to 7 in the scope of patent application. An infrared shielding film for solid-state imaging elements, which essentially contains only one or two organic pigments, and satisfies the following (A) to (C), (A) the transmittance in the range of 430nm or more and 580nm or less The average value is 75% or more, (B) the average transmittance in the range of wavelength 700nm or more and 900nm or less is 16.5% or less, (C) the transmittance under the wavelength of 1200nm is 10% or less, the organic dye Is a phthalocyanine compound represented by the following formula (1);

In formula (1), multiple Rs are each independently an alkyl group or an aryl group; multiple Xs are each independently a hydrogen atom, a halogen atom or an alkyl group; multiple Xs may also be bonded to each other and to these groups The carbon chains of together form an aromatic ring; M is two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal derivative; multiple n are each independently an integer of 3-6. The infrared shielding film as described in item 9 of the scope of patent application, wherein (D) the uniform transmittance of visible light represented by the following formula is 10% or less, Visible light uniform transmittance=((average value of transmittance in the range of wavelength 430nm or more and 580nm or less-the lowest value of transmittance in the range of wavelength 430nm or more and 580nm or less)/wavelength of 430nm or more and 580nm or less The average value of the transmittance in the range}×100(%). The infrared shielding film according to item 9 or 10 of the scope of patent application, which further contains an infrared shielding agent, and the infrared shielding agent is a metal oxide, a copper compound, or a combination of these. The infrared shielding film according to the 11th patent application, wherein the infrared shielding agent is cesium tungsten oxide. A solid-state imaging element having the infrared shielding film according to any one of the eighth to twelfth patent applications.

Images