JP6922361B2 - Composition for solid-state image sensor, infrared shielding film and solid-state image sensor - Google Patents

Description

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

Video cameras, digital cameras, mobile phones with camera functions, and the like are equipped with solid-state image sensors such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary MOS) image sensors. The sensitivity of the photodiode provided in these solid-state image sensors ranges from the visible light region to the infrared region. For this reason, the solid-state image sensor is provided with a filter for blocking infrared rays. With this infrared blocking filter, the sensitivity of the solid-state image sensor can be corrected so as to approach the human visual sensitivity.

The infrared blocking filter contains a dye or pigment as an infrared shielding agent. The infrared shielding agent is required to have a property of absorbing infrared rays while sufficiently transmitting visible light. As one of such infrared shielding agents, in particular, the use of 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 the phthalocyanine compound, the visible light transmittance and the infrared shielding property are not sufficiently satisfied. Therefore, in order to exhibit the above-mentioned good characteristics, for example, a large number of kinds of infrared ray shielding agents may be mixed and used. The use of such a large number of types of infrared shielding agents also causes a decrease in productivity such as high cost. Further, in the conventional infrared blocking filter using a phthalocyanine compound, the variation in transparency may be large in the visible light region. Even in such a case, good visual sensitivity correction is not performed.

Japanese Unexamined Patent Publication No. 2008-201952

However, even in the conventional infrared blocking filter for a solid-state image sensor using a phthalocyanine compound, the visible light transmittance and the infrared shielding property are not sufficiently satisfied. Therefore, in order to exhibit the above-mentioned good characteristics, for example, a large number of kinds of infrared ray shielding agents may be mixed and used. The use of such a large number of types of infrared shielding agents also causes a decrease in productivity such as high cost. Further, in the conventional infrared blocking filter using a phthalocyanine compound, the variation in transparency may be large in the visible light region. Even in such a case, good visual sensitivity correction is not performed.

The present invention has been made based on the above circumstances, and an object of the present invention is to have both good visible light transmission and infrared shielding property even when the types of organic dyes contained are small. A composition for a solid-state image sensor that can form an optical filter for a solid-state image sensor, and a solid-state image sensor that has both good visible light transmission and infrared shielding properties even when the types of organic dyes contained are small. It is an object of the present invention to provide an infrared shielding film for an element, and a solid-state image sensor 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 to solve the above problems is a composition for a solid-state image sensor containing a phthalocyanine compound represented by the following formula (1) (hereinafter, also referred to as "[A] phthalocyanine compound").

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

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

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

Yet another invention made to solve the above problems is a solid-state image sensor having the infrared shielding film (I) or the infrared shielding film (II).

According to the present invention, a solid-state image sensor capable of forming an optical filter for a solid-state image sensor having both good visible light transmission and infrared shielding property even when the type of organic dye contained is small. The composition for use, an infrared shielding film for a solid-state image sensor having good visible light transmittance and infrared shielding property even when the type of organic dye contained is small, and such an infrared shielding film. A solid-state image sensor can be provided.

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

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

<Composition for solid-state image sensor>
The composition for a solid-state image sensor according to an embodiment of the present invention (hereinafter, also simply referred to as “composition”) contains the [A] phthalocyanine compound. The composition preferably further contains a metal oxide, a copper compound (excluding the [A] phthalocyanine compound), or a combination thereof, [B] an infrared shielding agent.

([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 region (for example, a wavelength region of 430 nm or more and 580 nm or less), while has high shielding property in the near infrared region (for example, a wavelength region of 700 nm or more and 900 nm or less). Since the composition contains such a [A] phthalocyanine compound, an optical filter having good visible light transmittance and infrared shielding property is formed even when the number of types of organic pigments contained is small. can do. Further, since the composition contains such a [A] phthalocyanine compound, it is possible to form an optical filter having high uniform transparency in the visible light region.

In the formula (1), each of the plurality of Rs is independently an alkyl group or an aryl group. Each of the plurality of Xs is independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs 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. The plurality of ns are independently integers of 3 to 6.

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

Examples of the aryl group represented by R include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthrasenyl group and the like.

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

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

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

A plurality of Xs may be connected to each other. Usually, of a plurality of Xs, two Xs bonded to the same benzene ring are bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. Examples of the aromatic ring formed include a benzene ring, a naphthalene ring, an anthracene ring and the like. The hydrogen atoms of these aromatic rings may be substituted with hydrocarbon groups or other substituents.

As the X, a hydrogen atom is preferable.

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

Here, the derivative of a metal atom means an atomic group containing a metal atom. A trivalent metal atom is a metal atom that can become a trivalent cation. Examples of the trivalent metal atom include Al and In. A tetravalent metal atom is a metal atom that can become a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, Sn and the like. The metal atom also includes a metalloid atom. Derivatives of the trivalent or tetravalent metal atom represented by M are 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 can be mentioned.

As the 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.

As the lower limit of n, 4 is preferable. 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 even 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, further preferably 800 nm, and even 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 better visible light transmission and infrared shielding property.

[A] The method for synthesizing the phthalocyanine compound is not particularly limited, and known methods can be combined for synthesis. For example, it can be synthesized according to the following scene1.

In scene1, R, X, M and n are synonymous with the formula (1).

As the dicyano compound in the scene 1, a plurality of types of dicyano compounds having different _{substituents (RO (CH 2} ) _{n − or X) may be used.} ^Examples of the source of the metal ion represented by M 2+ include various metal salts such as acetate, chloride, bromide, nitrate and sulfate. By mixing the compound represented by the above formula (0) with a metal salt or the like in a solvent, the [A] phthalocyanine compound represented by the above formula (1) can be obtained. Examples of the solvent include aromatic hydrocarbons (benzene, toluene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), chlorinated hydrocarbons (methylene chloride, chloroform, dichloroethane, etc.), DMF, DMSO, acetonitrile, THF, N. -Methylpyrrolidone, dioxane, alcohol (methanol, ethanol, etc.) and the like can be mentioned.

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

[A] The phthalocyanine compound may be used alone or in combination of two or more. However, 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 type of phthalocyanine compound can exhibit good visible light transmittance and infrared shielding property. Therefore, by reducing the number of types of the [A] phthalocyanine compound used, it is possible to increase productivity while exhibiting good visible light transmittance and infrared shielding property.

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

[B] Examples of the metal oxide as an infrared shielding agent include tungsten oxide compounds, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), and zirconia (Zirconia). ZrO ₂ ), spinel (MgAl ₂ O ₄ ) and the like can be mentioned.

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

[B] As the infrared shielding agent, a metal oxide is preferable, and a tungsten oxide-based compound is more preferable. Tungsten oxide compounds are infrared shields that have high absorption (that is, high shielding against infrared rays) for infrared rays (particularly infrared rays with a wavelength of about 800 nm or more and 1200 nm or less) and low absorption for visible light. be. Therefore, by containing the tungsten oxide-based compound in the composition, it is possible to improve the infrared shielding property while maintaining the good visible light transmittance of the obtained optical filter. [B] As the infrared shielding agent, one type may be used alone, or two or more types may be mixed and used.

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

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

Examples of the metal element represented by A in the above formula (2) include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt and 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 the above A, an alkali metal is preferable, Rb and Cs are more preferable, and Cs is further preferable. That is, the metal oxide is more preferably tungsten cesium oxide.

When x in the above formula (2) is 0.001 or more, infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, more preferably 0.1. On the other hand, when x is 1.1 or less, it is possible to more reliably avoid the formation of an impurity phase in the tungsten oxide-based compound. 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 , and Ba _0.33 WO _3. 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 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, further preferably 50 nm, and even more preferably 30 nm. When the average particle size is not more than the above upper limit, the visible light transmission can be further enhanced. On the other hand, for reasons such as ease of handling during manufacturing, the average particle size of the [B] infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

[B] The infrared shielding agent can be synthesized by a known method, but is available 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. The tungsten oxide-based compound is also available 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 of the composition is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass. The lower limit of this content is further preferably 20% by mass, more preferably 30% by mass. On the other hand, as the upper limit of this content, 70% by mass is preferable, 65% by mass is more preferable, and 60% by mass is further preferable. [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 obtained optical filter are more well balanced.

As 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, 2 is preferable, 3 is preferable, 5 is more preferable, and 10 is more preferable. Even more preferable. On the other hand, as the upper limit of this mass ratio ([B] / [A]), 40 is preferable, 30 is more preferable, and 20 is further preferable. By setting the content ratio of the [A] phthalocyanine compound and the [B] infrared shielding agent within the above range, the visible light transmittance and the infrared shielding property of the obtained optical filter can be better balanced.

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

[C] Dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, and sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, (meth) acrylic dispersants and the like can be mentioned. Among these, a (meth) acrylic dispersant is preferable. [C] The dispersant is preferably a block copolymer.

[C] Dispersants are commercially available, for example, as (meth) acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK). ), As a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (all manufactured by Big Chemie (BYK)). 76500 (manufactured by Lubrizol Co., Ltd.), Solsparse 24000 (manufactured by Lubrizol Co., Ltd.) as a polyethyleneimine-based dispersant, Ajispar PB821, Ajispar PB822, Ajispar PB880, Ajispar PB881 (above, In addition to Ajinomoto Fine Techno Co., Ltd.), BYK-LPN21324 (manufactured by Big Chemie (BYK)) and the like can be mentioned.

[C] As the lower limit of the amine value of the dispersant, 10 mgKOH / g is preferable, 40 mgKOH / g is more preferable, and 80 mgKOH / g is further preferable. On the other hand, as the upper limit of the amine value, 300 mgKOH / g is preferable, 200 mgKOH / g is more preferable, and 150 mgKOH / g is further preferable. By using a 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 HCl and equivalent KOH required to neutralize 1 g of the dispersant solid content.

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

([D] Polymerizable compound)
The composition preferably further contains the [D] polymerizable compound. When the composition contains the [D] polymerizable compound, good curability and good heat resistance of the obtained optical filter can be exhibited. [D] The polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. [D] As the polymerizable compound, a compound having two or more (meth) acryloyl groups and a compound having two or more N-alkoxymethylamino groups are preferable, and the compound has two or more (meth) acryloyl groups. Compounds are more preferred. [D] The polymerizable compound can be used alone or in admixture of two or more.

Examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a caprolactone-modified polyfunctional (meth) acrylate. , Alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having a hydroxyl group and polyfunctional isocyanate, (meth) acrylate having a hydroxyl group and acid anhydride. Examples thereof include a polyfunctional (meth) acrylate having a carboxyl group, which is a reaction product with and the like.

Here, examples of the above-mentioned aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Aliphatic polyhydroxy compounds having a trivalent or higher valence 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. And so on. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutacon anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic dianhydride. Examples thereof include tetrabasic acid dianhydrides such as acid dianhydrides and benzophenone tetracarboxylic dianhydrides.

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, and 1 , 9-Nonandiol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclode Candi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol tri ( Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipenta Examples thereof include erythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and urethane (meth) acrylate compound.

Among the compounds having two or more (meth) acryloyl groups, a polyfunctional (meth) acrylate is preferable, and a polyfunctional (meth) acrylate having three or more and ten or less (meth) acryloyl groups is 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 a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Specific examples of compounds 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) glycoluryl and the like.

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

([E] Polymerization Initiator)
The composition preferably contains the [E] polymerization initiator. [E] Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but a photopolymerization initiator is preferable. This makes it possible to impart photosensitivity (radiation sensitivity) to the composition. The photopolymerization initiator refers to a compound that generates an active species capable of initiating the polymerization of the [D] polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. [E] The polymerization initiator may be used alone or in admixture of two or more.

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

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

Examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane. Examples thereof include -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4). -Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole and the like can be mentioned.

When a biimidazole compound is used, it is preferable to use a hydrogen donor in combination because 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 by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like. Amine-based hydrogen donors can be mentioned.

Examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of JP-A-57-6096 and JP-A-2003-23898.

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

When a photopolymerization initiator is used, a sensitizer may also be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethylamino. Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

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

(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. Of these, a polymer having a carboxy group (hereinafter, also referred to as “carboxy group-containing polymer”) is preferable. Examples of the carboxy group-containing polymer include an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter, also referred to as “unsaturated monomer (1)”) and other copolymerizable ethylene. Examples thereof include a copolymer with a sex unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (2)”).

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

Examples of the unsaturated monomer (2) include N-position-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide.
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether and acenaphthylene,
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2- 10) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (Meta) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (Meta) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) (Meta) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane,
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ,
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

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

When the composition contains a binder resin, the content of the binder resin can be usually 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, if desired.

Examples of the additive include a surfactant, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a residue improver, a developability improver and the like.

Examples of the surfactant include a fluorine surfactant, a silicone surfactant and the like. 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.

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane.

Antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-). 4-Hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2, 4,8,10-Tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned. The content of the antioxidant may 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.

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

Examples of the anti-aggregation agent include sodium polyacrylate and the like.

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- Examples thereof include 1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like.

Developable agents include succinate mono [2- (meth) acryloyloxyethyl], phthalate mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like. Can be mentioned.

(Other organic pigments, etc.)
The composition may contain a known organic dye other than the organic dye as the [A] phthalocyanine compound and the [B] copper compound which is an infrared shielding agent. Other organic dyes include diminium compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quaterylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrolopyrrole compounds, oxonor compounds, croconium compounds, hexaphyllin. Examples include compounds (excluding those containing a copper atom). Further, a phthalocyanine compound other than the [A] phthalocyanine compound and the [B] phthalocyanine compound as an infrared shielding agent can also be used.

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, further preferably 700 nm, further preferably 750 nm, and even more preferably 800 nm. On the other hand, as the upper limit of the maximum absorption wavelength of the [a] phthalocyanine compound, 900 nm is preferable, 850 nm is more preferable, 800 nm is further preferable, 750 nm is further preferable, and 700 nm is further preferable. 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, the visible light transmittance and the infrared shielding property of the obtained optical filter can be further enhanced. It is also possible to enhance the uniform visible light transmittance of the obtained optical filter. The [a] phthalocyanine compound also includes a [B] phthalocyanine compound as a copper compound which is an infrared shielding agent. [A] Examples of the phthalocyanine compound include various conventionally known phthalocyanine compounds.

The lower limit of the content of the [A] phthalocyanine compound in the total organic dye in the composition is preferably 50% by mass, more preferably 70% by mass, more preferably 80% by mass, and more preferably 90% by mass. Sometimes it is preferable, and sometimes 99% by mass is more preferable. As the organic dye, it may be preferable to substantially contain only the [A] phthalocyanine compound. By reducing the content of other organic dyes in this composition, the productivity can be increased. In addition, it is possible to enhance the uniform transmission of visible light in the obtained optical filter.

The number of types of the organic dye contained in the composition is preferably 3 or less, more preferably 2 or less, and even more preferably 1 type, including the [A] phthalocyanine compound. By reducing the number of types of organic dyes contained in this way, it is possible to improve productivity and also to improve the uniform transmission of visible light in the obtained optical filter. When two or more kinds of organic dyes are used, it is preferable to use the [A] phthalocyanine compound and a phthalocyanine compound other than the [A] phthalocyanine compound in combination.

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

Examples of such a 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, diethylene glycol monoethyl ether, and 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, etc. (poly) Alkylene glycol monoalkyl ethers,
Lactic acid 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, etc.
Chain ketones such as methyl ethyl ketone, 2-heptanone, 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, etc.
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, i butyrate 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,
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and lactams.

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

(Preparation method)
The method for preparing the composition is not particularly limited, and the composition can be prepared and adjusted 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 method of preparing a liquid, adding the [A] phthalocyanine compound and other components to the dispersion, and mixing them can be adopted. The dispersion liquid or the composition can be subjected to a filtration treatment, if necessary, to remove agglomerates.

<Infrared shielding film (I)>
The infrared shielding film (I) according to an embodiment of the present invention is an infrared shielding film for a solid-state image sensor formed from the composition for the solid-state image sensor. The optical filter for a solid-state image sensor having the infrared shielding film (I) has good visible light transmittance and infrared shielding property even when the types of organic dyes contained are small. Further, the infrared shielding film (I) is excellent in uniform transmission in the visible light region.

The infrared shielding film (I) is preferably incorporated in a solid-state image sensor as one component. In this case, the infrared shielding film (I) functions as an optical filter (infrared cut filter) by itself. It is preferable that the infrared shielding film (I) is incorporated in the solid-state image sensor because a large process margin can be obtained. When the infrared shielding film (I) is incorporated in the solid-state image sensor, the infrared shielding film (I) is, for example, on the outer surface side of the microlens of the solid-state image sensor, between the microlens and the color filter, and a color filter. It can be placed 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.

The optical filter may be one in which the infrared shielding film (I) is laminated on the surface of a transparent substrate. As the transparent substrate, glass, a transparent resin, or the like is adopted. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Such an optical filter is also suitably used as an infrared cut filter or the like in a solid-state image sensor.

The solid-state image sensor provided with the optical filter is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, personal digital assistants, personal computers, video games, medical devices, and the like.

The infrared shielding film (I) can be formed by, for example, the following method. First, the composition is applied onto the support, and then prebaked to evaporate the solvent to form a coating film. Next, after exposing this coating film, it is developed with a developing solution to dissolve and remove the unexposed portion of the coating film. Then, 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, it is not necessary to perform a curing treatment such as exposure. Further, it is not necessary to perform the developing process, and in this case, the infrared shielding film (I) which is not patterned can be formed.

The transparent substrate, microlens, color filter and the like correspond to the support to which the composition is applied. For the above coating, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), and a bar coating method can be adopted.

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

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

As the developer, an alkaline developer is generally used. Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonen or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After development, it is usually washed with water.

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

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

The lower limit of the average film thickness of the infrared shielding film (I) formed in this manner is usually 0.5 μm, preferably 1 μm. On the other hand, the upper limit of this 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 range, the balance between the visible light transmittance and the infrared shielding property becomes better. Further, as the suitable visible light transmittance and infrared transmittance of the infrared shielding film (I), the range of the infrared shielding film (II) described later can be applied.

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

The optical filter for a solid-state image sensor provided with the infrared shielding film (II) has both good visible light transmittance and infrared shielding property. Further, since the infrared shielding film (II) contains substantially only one or two kinds of organic dyes, it is easy to prepare and has high productivity. Here, "substantially containing only one or two kinds of organic dyes" means that the content ratio of one or two kinds of organic dyes in the total organic dyes contained is 90% by mass or more. Say something. This content ratio is preferably 99% by mass or more, and more preferably 99.9% by mass or more. It is preferable that the infrared shielding film (II) contains substantially only one kind of organic dye.

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

(A) 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%, more preferably 80%. When the average value of the transmittance is at least 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 and 900 nm or less is 16.5%, preferably 16%, more preferably 15.5%, further preferably 15%, still more preferably 14%. Sometimes. When the average value of the transmittance is not more than the above upper limit, good 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 the transmittance in the wavelength range of 430 nm or more and 580 nm or less to the average value (N) of the transmittance in the wavelength range of 700 nm and 900 nm or less is preferably 5. 2 is more preferable. On the other hand, the upper limit of this ratio may be 10, may be 8, or may be 6.5.

(C) The upper limit of the transmittance at a wavelength of 1200 nm is 10%, but is preferably 8%, more preferably 7%, and even more preferably 6.1%. When this transmittance is not more than the above upper limit, good infrared shielding property can be exhibited. 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 uniform visible light transmittance represented by the following formula is 10% or less. The upper limit of the uniform visible light transmittance is more preferably 9% and further preferably 8%. When the visible light uniform transmittance is not more than the above upper limit, the visible light transmittance can be made uniform, and better visual sensitivity correction can be performed. The lower limit of the uniform visible light transmittance is not particularly limited, but may be, for example, 1%, 3%, or 5%.

Visible light uniform transmittance = {(average value of transmittance in the range of wavelength 430 nm or more and 580 nm-minimum value of transmittance in the range of wavelength 430 nm or more and 580 nm) / average value of transmittance in the range of wavelength 430 nm or more and 580 nm or less) } × 100 (%)

The infrared shielding film (II) can be formed, for example, by the composition for a solid-state image sensor according to the embodiment of the present invention described above. The method for forming the infrared shielding film (II) is also the same as the method described above as the method for forming the infrared shielding film (I). However, the composition to be used contains substantially only one or two kinds of 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 represented by the above formula (1) ([A] phthalocyanine compound).

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

The infrared shielding film (II) preferably contains a polymer having a crosslinked structure. A polymer having such a crosslinked structure is formed by a polymerization (crosslinking) reaction of the above-mentioned [D] polymerizable compound, a polymer having a polymerizable group such as a polymerizable unsaturated bond in the 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. Such an infrared shielding film (II) can be obtained by subjecting the coating film of the composition to a curing treatment such as irradiation with radiation or heating. Such an infrared shielding film (II) can exhibit better hardness and heat resistance than, for example, a melt-molded film-like film. Further, such an infrared shielding film (II) has an advantage that it can be relatively easily obtained as a cured film having an arbitrary shape patterned via a mask or the like.

<Solid image sensor>
The solid-state image sensor according to an embodiment of the present invention is a solid-state image sensor having the infrared shielding film (I) or the infrared shielding film (II). Even when the type of organic dye contained is small, the solid-state image sensor has an infrared shielding film having good visible light transmittance and infrared shielding property, so that good luminosity factor correction is performed.

The solid-state image sensor 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. Further, a flattening layer may be provided between these layers. In the solid-state image sensor, light is incident from the microlens side. The incident light passes through the microlens and the color filter and reaches the photodiode. As for 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 image sensor, the infrared shielding film (I) or the infrared shielding film (II) is formed on the outer surface side of the microlens, between the microlens and the color filter, the color filter and the plurality of photodiodes. Can be provided between the layers on which the is arranged. 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. Even if another layer (flattening layer, etc.) is provided between the infrared shielding film (I) or the infrared shielding film (II) and the microlens, color filter, photodiode, or the like. good.

Specific examples of the solid-state image sensor include a CCD and CMOS as a camera module. The solid-state image sensor is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, personal digital assistants, personal computers, video games, medical devices, and the like.

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

<Synthesis example 1>
A phthalocyanine compound (A-1) (maximum absorption wavelength 735 nm) represented by the following formula was synthesized according to the above Scene1. As a starting material, 1,2-dicyano-3,6-di (4-methoxybutyl) benzene was used. Lithium pentoxide (solid lithium and pentanol-1-ol) was used as "1.base", and glacial acetic acid was used as "2.acid". Moreover, vanadyl salt was used as the salt which gives ^{M 2+.}

<Synthesis example 2>
A phthalocyanine compound (a-1) (maximum absorption wavelength 692 nm) represented by the following formula was synthesized using the methods described in paragraphs [0020] to [0025] (Example 1) of JP-A-05-25177.

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

Other dyes used are as follows.
-Compound (a-3): "FDN-002" manufactured by Yamada Chemical Industry Co., Ltd. (phthalocyanine compound: maximum absorption wavelength 807 nm)

<Synthesis example 4>
_{Tungsten cesium 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 tungsten cesium oxide, 13.11 parts by mass of "BYK-LPM6919" (solid content concentration 61% by mass, amine value 120 mgKOH / g) of Big Chemie as a dispersant, 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 zirconia beads having a diameter of 0.1 mm and dispersed with a paint shaker to obtain a dispersion having an average particle diameter (D50) of 19 nm. The average particle size was measured by the DLS method using a light scattering measuring device (“ALV-5000” manufactured by ALV of Germany).

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

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

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

Each composition was applied onto a glass substrate by a spin coating method so as to have a predetermined film thickness. Then, the coating film was heated at 100 ° C. for 120 seconds and exposed to ^{1000 mJ / cm 2 with an i-line stepper.} Then, by heating at 220 ° C. for 300 seconds, an infrared shielding film having an average film thickness of 1.4 to 1.6 μm was produced on a glass substrate. Each average film thickness is shown in Table 1. The film thickness was measured with a stylus type step meter (“Alpha Step IQ” manufactured by Yamato Scientific Co., Ltd.). Next, the transmittance of the infrared shielding film produced on the glass substrate in each wavelength region was measured using a spectrophotometer (“V-7300” manufactured by JASCO Corporation) in comparison with the glass substrate. 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 the wavelength (nm) and the vertical axis is the transmittance (%).

(Visible light transmission)
The average transmittance of 430-580 nm was calculated. If the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film decreases. In addition, the average transmittance was evaluated according to the following criteria.
A: 80% or more B: 70% or more and less than 80% C: less than 70%

(Infrared 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. In addition, the average transmittance was evaluated according to the following criteria.
A: Less than 15% B: 15% or more and less than 20% C: 20% or more

(Infrared shielding 2)
With regard to the transmittance at a wavelength of 1200 nm, it can be said that the transmittance is less than 15% and shows practically good infrared shielding property. 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, and the practical performance was estimated. 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 S / N ratio was evaluated according to the following criteria.
A: 5 or more and B: less than 5

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

As shown in Table 1 above, the infrared shielding films of Examples 1 to 3 have both good visible light transmittance and infrared shielding property (A or B), and also have uniform visible light transmittance. Excellent. Further, it can be seen that the infrared shielding films of Examples 1 to 3 are able to exhibit such good characteristics even though the organic dye is contained in only one or two kinds.

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

Claims (13)

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

(In the formula (1), the plurality of Rs are each independently an alkyl group or an aryl group. The plurality of Xs are each independently a hydrogen atom, a halogen atom or an alkyl group. , They may be bonded to each other to form an aromatic ring together with the carbon chains to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. N is an integer of 3 to 6 independently of each other.) The composition for a solid-state image sensor according to claim 1, further comprising a metal oxide, a copper compound (excluding the above-mentioned phthalocyanine compound), or an infrared shielding agent which is a combination thereof. The composition for a solid-state image sensor according to claim 2, wherein the infrared shielding agent is tungsten cesium oxide. The composition for a solid-state image sensor according to claim 2 or 3, wherein the content of the metal oxide, the copper compound, or a combination thereof is 1% by mass or more and 70% by mass or less with respect to the total solid content. The composition for a solid-state image sensor 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 image sensor according to any one of claims 1 to 5, wherein R in the above formula (1) is a linear or branched alkyl group having 1 to 12 carbon atoms. Claims 1 to 6 in which 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 a solid-state image sensor according to any one of the above items. An infrared shielding film for a solid-state image sensor formed from the composition for a solid-state image sensor according to any one of claims 1 to 7. Containing substantially only one or two organic dyes,
The following (A) meets - the (C),
An infrared shielding film for a solid-state image sensor in which the organic dye is a phthalocyanine compound represented by the following formula (1).
(A) The average value of the transmittance in the wavelength range of 430 nm or more and 580 nm or less is 75% or more (B) The average value of the transmittance in the wavelength range of 700 nm or more and 900 nm or less is 16.5% or less (C) The transmittance in the wavelength range of 1200 nm Is less than 10%

(In the formula (1), the plurality of Rs are each independently an alkyl group or an aryl group. The plurality of Xs are each independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs are independent. , They may be bonded to each other to form an aromatic ring together with the carbon chains to which they are bonded. M is a two hydrogen atom, a divalent metal atom, or a tri or tetravalent metal derivative. Are independently integers of 3 to 6). (D) The infrared shielding film according to claim 9, wherein the uniform visible light transmittance represented by the following formula is 10% or less.
Visible light uniform transmittance = {(average value of transmittance in the range of wavelength 430 nm or more and 580 nm-minimum value of transmittance in the range of wavelength 430 nm or more and 580 nm) / average value of transmittance in the range of wavelength 430 nm or more and 580 nm or less) } × 100 (%) The infrared shielding film according to claim 9 or 10, further comprising an infrared shielding agent which is a metal oxide, a copper compound, or a combination thereof. The infrared shielding film according to claim 11, wherein the infrared shielding agent is tungsten cesium oxide. A solid-state image sensor having an infrared shielding film according to any one of claims 8 to 12.

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