KR20180113914A - Composition for solid-state imaging device, infrared shielding film, and solid-state imaging device - Google Patents

Abstract

The present invention provides a composition for a solid-state imaging device, capable of forming an optical filter for a solid-state imaging device which has excellent visible light transmittance and infrared shielding properties even when the kind of organic pigment contained therein is small. The present invention relates to a composition for a solid-state imaging device containing a phthalocyanine compound represented by chemical formula (1). In chemical formula (1), each of a plurality of Rs is independently an alkyl group or an aryl group, and each of a plurality of Xs is independently a hydrogen atom, a halogen atom, or an alkyl group. The Xs may be combined with each other to form a direction ring together with a carbon chain with which the Xs are combined. In addition, M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or a tetravalent metal atom, and each of a plurality of ns is independently an integer of three to six.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for a solid-state imaging device, an infrared shielding film, and a solid-state imaging device,

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

2. Description of the Related Art Solid-state image pickup devices such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary MOS) image sensors are mounted on video cameras, digital cameras, mobile phones having camera functions and the like. The sensitivity of the photodiodes provided in these solid-state image pickup devices ranges from the visible light region to the infrared region. Therefore, in the solid-state image pickup device, a filter for blocking infrared rays is provided. With this infrared cut filter, the sensitivity of the solid-state image pickup device can be corrected so as to be close to human visibility.

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

However, even in the conventional infrared cut filter using a phthalocyanine compound, visible light transmittance and infrared ray shielding property are not sufficiently satisfied. For this reason, for example, a plurality of kinds of infrared shielding agents may be mixed and used in order to exhibit good properties. The use of such a plurality of kinds of infrared shielding agents may cause a decrease in productivity, such as a high cost. In addition, in a conventional infrared cut filter using a phthalocyanine compound, the transmittance of the infrared ray in the visible light region may vary greatly. Even in such a case, good visual sensitivity correction can not be performed.

Japanese Patent Application Laid-Open No. 2008-201952

However, the visible light transmittance and the infrared ray shielding property are not sufficiently satisfied even in the conventional infrared cut filter for the solid-state image pickup device using the phthalocyanine compound. For this reason, for example, a plurality of kinds of infrared shielding agents may be mixed and used in order to exhibit good properties. The use of such a plurality of kinds of infrared shielding agents may cause a decrease in productivity, such as a high cost. In addition, in a conventional infrared cut filter using a phthalocyanine compound, the transmittance of the infrared ray in the visible light region may vary greatly. Even in such a case, good visual sensitivity correction can not be performed.

The object of the present invention is to provide a solid state imaging device capable of forming an optical filter for a solid-state imaging element having good visible light transmittance and infrared shielding property even when the kind of organic dye contained therein is small, An infrared ray shielding film for a solid-state imaging element, which has good visible light transmittance and infrared ray shielding property even when the composition for an imaging device contains a small number of kinds of organic pigments, and a solid-state image pickup device having such an infrared ray shielding film.

The invention made to solve the above problems is a composition for a solid-state imaging element containing a phthalocyanine compound represented by the following formula (1) (hereinafter also referred to as "[A] phthalocyanine compound").

The plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X's are bonded to each other to form a bond, M is a hydrogen atom, a divalent metal atom, or a derivative of a metal atom of a trivalent or tetravalent metal, and n is, independently of each other, 3 to 6 carbon atoms, It is an integer.)

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

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

(A) an average value of transmittance in a wavelength range of from 430 nm to 580 nm is 75% or more

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

(C) a transmittance at a wavelength of 1200 nm of not more than 10%

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

According to the present invention, there is provided a composition for a solid-state imaging element capable of forming an optical filter for a solid-state imaging element having good visible light transmittance and infrared shielding property even when the kind of the organic coloring matter contained is small, It is possible to provide an infrared ray shielding film for a solid-state image pickup element having both good visible light transmittance and infrared ray shielding property, and a solid-state image pickup device having such an infrared ray shielding film.

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

Hereinafter, a composition for a solid-state imaging device, an infrared-ray 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 element>

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

([A] phthalocyanine compound)

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

In the formula (1), a plurality of R's are each independently an alkyl group or an aryl group. The plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. The plural 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 hydrogen atom, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. The plurality of n's are each independently an integer of 3 to 6.

Examples of the alkyl group represented by R include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, A straight chain or branched alkyl group.

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

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

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

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

The plurality of Xs may be coupled to each other. Generally, out of a plurality of X, two Xs bonded to the same benzene ring are bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. Examples of the aromatic ring to be formed include a benzene ring, a naphthalene ring, and an anthracene ring. The hydrogen atom of these aromatic rings may be substituted with a hydrocarbon group or other substituent.

As 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 which can be a divalent cation.

Here, a derivative of a metal atom refers to an atomic group containing a metal atom. The trivalent metal atom is a metal atom that can be a trivalent cation. Examples of the trivalent metal atom include Al and In. The tetravalent metal atom is a metal atom that can be a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, and Sn. The metal atom also includes a half metal atom. As the derivatives of the metal atom 3 or tetravalent represented by the above M, 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, and TiO.

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, .

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

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

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

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

Further, as the dicyano compound in Scheme 1, plural kinds of dicyano compounds different in substituent (RO (CH ₂ ) _n - or X) may be used. Examples of the source of metal ions represented by M ^{2 +} include various metal salts such as acetate, chloride, bromide, nitrate and sulfate. The [A] phthalocyanine compound represented by the formula (1) can be obtained by mixing the compound represented by the formula (0) and a metal salt or the like in a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and cyclohexane, chlorinated hydrocarbons such as methylene chloride, chloroform and dichloroethane, DMF, DMSO, acetonitrile, THF, Dioxane, alcohol (methanol, ethanol, etc.), and the like.

The lower limit of the content of the [A] phthalocyanine compound in the total solid content in the composition is preferably 0.1% by mass, more preferably 0.5% by mass, 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, even more preferably 10% by mass, still more preferably 5% by mass. When the content of the phthalocyanine compound [A] is within the above range, the visible light transmittance and the infrared ray shielding property of the obtained optical filter become a better balance.

The phthalocyanine compound [A] may be used singly 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. The [A] phthalocyanine compound can exhibit good visible light transmittance and infrared ray shielding property with only one kind. Therefore, by decreasing the number of kinds of the [A] phthalocyanine compound used, the productivity can be enhanced while exhibiting good visible light transmittance and infrared ray shielding property.

([B] infrared shielding agent)

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

[B] As the metal oxide as an infrared masking agent, for example a tungsten-based compound oxide, quartz (SiO _2), magnetite (Fe ₃ O _4), alumina (Al ₂ O _3), titania (TiO _2), zirconia (ZrO ₂ ), Spinel (MgAl ₂ O ₄ ), and the like.

[B] Copper compounds as infrared shielding agents include copper phthalocyanine compounds and other copper complexes. Examples of the copper phthalocyanine compound include copper phthalocyanine, chlorophthalocyanine chloride, copper phthalocyanine bromide, and copper phthalocyanine bromide.

[B] As the infrared shielding agent, a metal oxide is preferable, and a tungsten oxide compound is more preferable. The tungsten oxide compound is an infrared shielding agent that has a high absorption (that is, a high shielding property against infrared rays) for infrared rays (particularly infrared rays having a wavelength of about 800 nm to 1200 nm) and a low absorption for visible light. Therefore, by containing the tungsten oxide-based compound in the composition, the obtained optical filter can improve the infrared ray shielding property while maintaining good visible light transmittance. [B] The infrared shielding agents may be used singly or in combination of two or more kinds.

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

A _x W0 _y (2)

In the formula (2), A is a metal element. 0.001? X? 1.1. 2.2? Y? 3.0.

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

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

When x is 0.001 or more in the formula (2), 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, generation of an impurity phase in the tungsten oxide compound can be more reliably avoided. 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 as a material can be further improved. The lower limit of y is preferably 2.5. On the other hand, since 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 and the like, and Cs _{0 . 33} WO ₃ and Rb _{0 . 33} WO ₃ is preferred, and Cs _{0 . 33} WO ₃ is more preferred.

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

[B] The infrared shielding agent can be synthesized by a known method, but is available as a commercial product. When the metal oxide is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by, for example, a method of heat-treating a 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 microparticles such as &quot; YMF-02 &quot; of Sumitomo Mitsui Chemicals, Inc., for example.

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

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

([C] dispersant)

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

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

Dispersing agent [C] is commercially available and is commercially available, for example, as a (meth) acrylic dispersant, such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK- Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 and Disperbyk-2164 (manufactured by BYK), Sorbus 76500 Azisper PB822, Ajisper PB880, Ajisper PB881 (or more) as a polyethylene-based dispersing agent, as a polyethylene imine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Corporation) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), and BYK-LPN21324 (manufactured by BYK).

The lower limit of the amine value of the [C] dispersant is preferably 10 mgKOH / g, more preferably 40 mgKOH / g, and even 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 even more preferably 150 mgKOH / g. By using such a dispersant having an amine value, the dispersibility of the [B] infrared shielding agent is improved, and the visible light transmittance and the infrared ray shielding property of the obtained optical filter can be further improved. Also, "amine value" is the number of mg of KOH equivalent to HCl required to neutralize 1 g of solid dispersant.

The lower limit of the content of the [C] dispersant is preferably 5 parts by mass, more preferably 15 parts by mass, and further preferably 30 parts by mass, per 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 even more preferably 60 parts by mass.

([D] polymerizable compound)

The composition preferably further comprises a [D] polymerizable compound. When the composition contains the [D] polymerizable compound, good curability and good heat resistance of the resulting optical filter can be exhibited. [D] Polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group and an N-alkoxymethylamino group. As the [D] polymerizable compound, a compound having two or more (meth) acryloyl groups and a compound having two or more N-alkoxymethylamino groups are preferable, and a compound having two or more (meth) desirable. [D] The polymerizable compound may be used alone or in combination of two or more.

Examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate such as a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, A polyfunctional urethane (meth) acrylate such as a reaction product of a (meth) acrylate modified with a seed, a reaction product of a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, a reaction product of a (meth) acrylate having a hydroxyl group with an acid anhydride (Meth) acrylate having a carboxyl group such as methacrylate and the like.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol , And the like can be given as examples of the aliphatic polyhydroxy compound. 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. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and anhydrides of pyromellitic acid anhydride, biphenyltetracarboxylic acid Dianhydride, benzophenone tetracarboxylic acid dianhydride, and the like.

Specific examples of the compound having two or more (meth) acryloyl groups include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) (Meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol (meth) acrylate, tetraethylene glycol di 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) methacrylate, Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di (pentaerythritol tetra (meth) acrylate, Pentaerythritis (Meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, urethane (meth) acrylate Compounds and the like.

Among the compounds having two or more (meth) acryloyl groups, polyfunctional (meth) acrylates are preferable, and polyfunctional (meth) acrylates having 3 or more and 10 or less (meth) acryloyl groups are more preferable Do. 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) N, N ', N'-tetra (alkoxymethyl) glycoluril, and the like.

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

([E] polymerization initiator)

The composition preferably contains a polymerization initiator [E]. As the polymerization initiator [E], a photopolymerization initiator, a thermal polymerization initiator and the like can be mentioned, but a photopolymerization initiator is preferred. Thus, the photosensitive composition (radiation-sensitive) can be imparted to the composition. The photopolymerization initiator refers to a compound which generates active species capable of initiating polymerization of the [D] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray. [E] The polymerization initiator may be used alone or in combination of two or more.

Examples of the polymerization initiator [E] include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, , an? -diketone compound, a polynuclear quinone compound, a diazo compound, an imidosulfonate compound, an onium salt compound, and the like. Among them, a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound are preferable, and an O-acyloxime compound is more preferable.

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

Examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Phenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

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

In the case of using a nonimidazole-based compound, it is preferable to use a hydrogen donor in combination in order to improve the sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; And amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Examples of the triazine compound include compounds described in paragraphs [0063] to [0065] of Japanese Patent Publication Nos. 57-6096 and 2003-238898.

Examples of the O-acyloxime compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime), ethanone- 1- [ -9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol- -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [ Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime). NCI-831 and NCI-930 (manufactured by ADEKA Corporation), OXE-03 and OXE-04 (manufactured by BASF Co., Ltd.) can be used as a commercially available product of O-acyloxime compound.

When a photopolymerization initiator is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

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

(Binder resin)

The composition may further contain a binder resin. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a &quot; carboxyl group-containing polymer &quot;) is preferable. Examples of the carboxyl group-containing polymer include copolymers of an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as &quot; unsaturated monomer (1) &quot;) and a copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as &quot; unsaturated monomer Quot;). &Lt; / RTI &gt;

Examples of the unsaturated monomer (1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono , p-vinylbenzoic acid, and the like.

As the unsaturated monomer (2), for example,

Position-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, and the like; aromatic vinyl monomers such as styrene, alpha -methylstyrene, p-hydroxystyrene, p-hydroxy- alpha -methylstyrene, Aromatic vinyl compounds such as diesters and acenaphthylene,

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, propylene glycol Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) Meth) acrylate, 3,4-epoxide Cyclohexylmethyl (meth) acrylate, 3 - [(meth) acryloyloxyethyl methyl] oxetane, 3-ethyl-3-oxetane, such as (meth) acrylic acid esters [(meth) acryloyl-oxy-methyl],

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Such as vinyl ether,

And macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

As the binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in its side chain may also be used. A 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 may be generally 10 parts by mass or more and 10,000 parts by mass or less based on 100 parts by mass of the [A] phthalocyanine compound.

(additive)

The composition may contain various additives as required.

Examples of the additive include surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, residue improvers, and development improvers.

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

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

Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis [3- (3,5- -Butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3- -Dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionate ] And the like. The content of the antioxidant is usually 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the [A] phthalocyanine compound.

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

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

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

Examples of the developability improver include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono .

(Other organic pigments, etc.)

The composition may contain a known organic dye other than the organic dye as the [A] phthalocyanine compound and the copper compound as the [B] infrared shielding agent. Examples of other organic dyes include a diamine compound, a squarylium compound, a cyanine compound, a naphthalocyanine compound, a quaternary compound, an aminium compound, an iminium compound, an azo compound, an anthraquinone compound, a porphyrin compound, a pyrrolopyrrole compound, Norbornene compounds, croconium compounds, hexapyrine compounds and the like (excluding those containing copper atoms). In addition, a phthalocyanine compound other than the [A] phthalocyanine compound and the [B] infrared shielding agent may be used.

It is also preferable to use a combination of the [A] phthalocyanine compound and a phthalocyanine compound other than the [A] phthalocyanine compound (hereinafter also referred to as "[a] phthalocyanine compound"). The lower limit of the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 600 nm, more preferably 650 nm, further preferably 700 nm, more 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 more preferable, 750 nm is more preferable, and 700 nm is more preferable. The lower limit of the difference between the maximum absorption wavelength of the phthalocyanine compound [A] and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm, and further preferably 50 nm. On the other hand, as the upper limit of the difference, 100 nm is preferable, 80 nm is more preferable, and 50 nm is more preferable. By using these phthalocyanine compounds in combination, the visible light transmittance and the infrared ray shielding property of the optical filter obtained can be further increased. It is also possible to increase the visible light uniformity 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. As the [a] phthalocyanine compound, conventionally known various phthalocyanine compounds may be mentioned.

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, even more preferably 80% by mass, more preferably 90% In some cases, 99% by mass is more preferable. As the organic coloring matter, it may be preferable to contain substantially only the [A] phthalocyanine compound. The composition of the present invention can increase productivity by reducing the content of other organic pigments. It is also possible to increase the visible light uniform transmittance of the obtained optical filter.

The number of kinds of organic pigments contained in the composition also includes the [A] phthalocyanine compound, preferably 3 or less, more preferably 2 or less, and more preferably 1 species. Even when the number of kinds of the organic pigments contained in this way is reduced, productivity can be increased and the visible light uniform transmittance of the obtained optical filter can be increased. When two or more organic pigments are used, it is preferable to use a combination of the [A] phthalocyanine compound and a phthalocyanine compound other than the [A] phthalocyanine compound.

(menstruum)

This composition is usually prepared as a liquid composition containing a solvent (dispersion medium). The solvent may be appropriately selected and used as long as it is dispersible or dissolving other components, does not react with these components, and has appropriate volatility.

As such a solvent, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether,

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 and cyclohexanol,

Keto alcohols such as diacetone alcohol,

Ethylene glycol monomethyl ether acetate, 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 (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate,

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

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

Propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters,

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate,

Aromatic hydrocarbons such as toluene and xylene,

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

And the like.

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. When the solid content concentration is in the above range, the dispersibility, stability, coating property and the like become better.

(Preparation method)

The method for preparing the composition is not particularly limited and may be adjusted by mixing the components. For example, when the composition contains a metal oxide as an infrared shielding agent and a [C] dispersant, first, a dispersion containing an [B] infrared shielding agent, a [C] dispersant and a solvent is prepared , Adding the [A] phthalocyanine compound or other components to the dispersion, and mixing the mixture. The dispersion or the composition can be subjected to filtration treatment as necessary to remove the aggregates.

&Lt; Infrared shielding film (I) >

An infrared ray shielding film (I) according to an embodiment of the present invention is an infrared ray shielding film for a solid state image pickup device formed of the composition for a solid state imaging device. The optical filter for a solid-state imaging element having the infrared ray shielding film (I) combines good visible light transmittance and infrared ray shielding property even when the kind of the organic dye contained therein is small. Further, the infrared ray shielding film (I) is excellent in uniform transmittance in the visible light region.

It is preferable that the infrared ray shielding film (I) is a constituent member and is incorporated in the solid-state image pickup device. In this case, the infrared ray shielding film I functions as an optical filter (infrared cutoff filter) as a single unit. Since the infrared ray shielding film I is assembled to the solid-state image pickup device, a large process margin can be obtained, which is preferable. When the infrared ray shielding film I is assembled to the solid-state image pickup device, the infrared ray shielding film I is formed on the outer surface side of the microlenses of the solid-state image pickup device, between the microlenses and the color filter, And the like. It is preferable that the infrared ray shielding film (I) is laminated between the microlens and the color filter or between the color filter and the photodiode.

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

The solid-state image pickup device having the optical filter is useful for a digital still camera, a camera for a cellular phone, a digital video camera, a PC camera, a surveillance camera, an automobile camera, a portable information terminal, a personal computer, a video game,

The infrared ray shielding film (I) can be formed, for example, by the following method. First, after coating the composition on a support, prebaking is performed and the solvent is evaporated to form a coating film. Subsequently, the coated film is exposed and developed using a developer to dissolve and remove the unexposed portion of the coated film. Thereafter, by post-baking, the 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, a curing treatment such as exposure may not be performed. Further, the development processing need not be performed, and in this case, the unpatterned infrared ray shielding film I can be formed.

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

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

Examples of the light source of radiation used for exposure of the coating film include a lamp 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, XeCl excimer laser, and nitrogen laser. As an exposure light source, an ultraviolet LED may be used. The wavelength is preferably in the range of 190 nm to 450 nm. Of radiation exposure dose, in general, is about 10J / m ² or more 50,000J / m ² or less.

As the developer, an alkaline developer is generally used. Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -Diazabicyclo- [4.3.0] -5-nonene and the like are preferable. A water-soluble organic solvent such as methanol, ethanol or the like or a surfactant may be added in an appropriate amount to the alkali developing solution. After the development, it is usually washed with water.

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

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

The lower limit of the average film thickness of the infrared ray shielding film I thus formed is usually 0.5 占 퐉 and preferably 1 占 퐉. On the other hand, the upper limit of the average film thickness is usually 5 占 퐉, preferably 3 占 퐉. When the average film thickness of the infrared ray shielding film (I) is in the above range, the balance between the visible light transmittance and the infrared ray shielding property becomes better. The visible light transmittance and the infrared transmittance of the infrared ray shielding film I can be applied to the range of the infrared ray shielding film (II) described later.

<Infrared shielding film (II)>

The infrared ray shielding film (II) according to one embodiment of the present invention is an infrared ray shielding film for a solid-state imaging device containing substantially one or two kinds of organic dyes and satisfying the following (A) to (C).

(A) an average value of transmittance in a wavelength range of from 430 nm to 580 nm is 75% or more

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

(C) a transmittance at a wavelength of 1200 nm of not more than 10%

The optical filter for a solid-state imaging element including the infrared ray shielding film (II) has good visible light transmittance and infrared ray shielding ability. Further, since the infrared shielding film (II) contains substantially only one or two organic pigments, it is easily prepared and has high productivity. Here, the phrase &quot; substantially containing only one kind or two kinds of organic dyes &quot; means that the content ratio of one or two kinds of organic dyes in the total organic dyes contained is 90 mass% or more. The content thereof 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 organic dye.

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

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

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

The lower limit of the ratio (S / N ratio) of the average value (S / N) of the transmittance in the wavelength range of 430 nm to 580 nm to the mean value (N) of the transmittance in the wavelength range of 700 nm to 900 nm is preferably 5 , And 5.2 are more preferable. On the other hand, the upper limit of the ratio is 10, which is 8, or 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 further preferably 6.1%. When the transmittance is not more than the upper limit, good infrared ray shielding property can be exhibited. On the other hand, the lower limit of the transmittance may be, for example, 3%, 5% or 5.5%.

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

(D) a visible light transmittance of not more than 10%

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

(Average value of transmittance in a wavelength range of 430 nm to 580 nm - minimum value of transmittance in a wavelength range of 430 nm to 580 nm) / (average value of transmittance in a wavelength range of 430 nm to 580 nm) x 100 (%)

The infrared shielding film (II) can be formed by, for example, a composition for a solid-state imaging element, which is one embodiment of the present invention described above. The method of forming the infrared ray shielding film (II) is also the same as the above-described method of forming the infrared ray shielding film (I). However, in the composition to be used, substantially one or two kinds of organic dyes are contained, and at least the [A] phthalocyanine compound corresponds to an organic dye. That is, in the infrared ray shielding film (II), it is preferable that the organic dye is a phthalocyanine compound represented by the formula (1) ([A] phthalocyanine compound).

The preferable form of the composition for a solid-state imaging element for forming the infrared shielding film (II) is also the same as the composition for the solid-state imaging element described above. That is, it is preferable that the infrared ray 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. It is also preferable that the infrared shielding agent [B] is tungsten oxide. Other preferable forms of the infrared shielding film (II) are the same as those of the infrared shielding film (I) formed of the composition for the solid-state imaging element.

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

<Solid-state image sensor>

A solid-state image pickup device according to an embodiment of the present invention is a solid-state image pickup device having the infrared ray shielding film (I) or the infrared ray shielding film (II). Since the solid-state image pickup device has an infrared ray shielding film having good visible light transmittance and infrared ray shielding property even when the kind of the organic dye contained therein is small, good visual sensitivity correction is performed.

The solid-state image pickup device generally has a structure in which a layer in which a plurality of photodiodes are arranged, a color filter, and a microlens are stacked in this order. A planarization layer may be provided between these layers. In this solid-state image pickup device, light is incident from the microlens side. The incident light passes through the microlens and the color filter, and reaches the photodiode. The color filter is configured such that only light of a specific wavelength range is transmitted through each of the filters of R (red), G (green), and B (blue), for example.

In the solid-state image pickup device, the infrared ray shielding film (I) or the infrared ray shielding film (II) is arranged on the outer surface side of the microlens, between the microlens and the color filter, And the like. It is preferable that the infrared ray shielding film (I) or the infrared ray shielding film (II) is laminated between the microlens and the color filter or between the color filter and the photodiode. Further, another layer (a planarization layer or the like) may be provided between the infrared ray shielding film I or the infrared ray shielding film II and the microlens, the color filter, the photodiode, and the like.

Specific examples of the solid-state image pickup device include a CCD or a CMOS as a camera module. The solid-state image pickup device is useful for a digital still camera, a camera for a cellular phone, a digital video camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a personal computer, a video game,

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

&Lt; Synthesis Example 1 &

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

&Lt; Synthesis Example 2 &

A phthalocyanine compound (a-1) (maximum absorption wavelength of 692 nm) represented by the following formula was synthesized using the method described in paragraphs [0020] to [0025] (Example 1) of Japanese Patent Application Laid-Open No. 05-25177.

&Lt; Synthesis Example 3 &

A phthalocyanine compound (a-2) (maximum absorption wavelength of 728 nm) represented by the following formula was synthesized using the method described in paragraph [0075] (Example 4) of Japanese Patent Application Laid-Open No. 2016-204536.

The other pigments used are as follows.

Compound (a-3): &quot; FDN-002 &quot; (phthalocyanine compound: maximum absorption wavelength: 807 nm) manufactured by Yamada Kagaku Kogyo Co.,

&Lt; Synthesis Example 4 &

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

[Manufacturing Example]

25.00 parts by mass of the cesium tungsten oxide, 13.11 parts by mass of "BYK-LPM 6919" (trade name, solid content concentration of 61% by mass, amine value of 120 mgKOH / g) of Big Chemie as a dispersing agent and 61.89 parts by mass of cyclopentanone (CPN) . These were charged into a container together with 2000 parts by mass of zirconia beads having a diameter of 0.1 mm and dispersed in a paint shaker to obtain a dispersion having an average particle diameter (D50) of 19 nm. The average particle diameter was measured by the DLS method using a light scattering measurement apparatus ("ALV-5000" manufactured by ALV Co., Germany).

[Example 1]

, 0.75 parts by mass of a phthalocyanine compound (A-1), and 7.01 parts by mass of a polymerizable compound "KAYARAD DPHA" (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., 0.70 part by mass of "NCI-930" (O-acyloxime compound) of ADEKA as a polymerization initiator, 0.02 part by mass of "FTX-218D" (fluorine surfactant) manufactured by NEOS CORPORATION as a surfactant, "Irganox1010 (Phenol-based antioxidant) and 41.50 parts by mass of cyclopentanone (CNP) as a solvent were weighed in a vessel and mixed by a stirrer. 200 mL of this mixture was pressure-filtered at 0.5 MPa for 3 minutes using a PTFE (polytetrafluoroethylene) filter of 0.5 mu m to obtain a composition of Example 1.

[Examples 2 to 3, 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 changed as shown in Table 1.

[evaluation]

Each composition obtained was used and evaluated as follows. The evaluation results are shown in Table 1.

Each composition was coated on a glass substrate by a spin coating method so as to have a predetermined film thickness. Thereafter, the coating film is heated at 100 ℃ 120 seconds, and was subjected to the exposure such that the 1000mJ / cm ² by an i-line stepper. And then heated at 220 DEG C for 300 seconds to prepare an infrared ray shielding film having an average film thickness of 1.4 to 1.6 mu m on the glass substrate. The average film thicknesses are shown in Table 1. Further, the film thickness was measured by a contact type step system (&quot; alpha step IQ &quot; by Yamato Chemical Co., Ltd.). Subsequently, the transmittance in each wavelength region of the infrared shielding film formed on the glass substrate was measured using a spectrophotometer ("V-7300" manufactured by Nihon Bunko Co., Ltd.) relative to the glass substrate. From the obtained spectrum, evaluation was carried out according to the following evaluation criteria. The transmission spectrum of the infrared ray shielding film of Example 1 is shown in Fig. 1, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the transmittance (%).

(Visible light transmittance)

An average transmittance of 430 to 580 nm was calculated. When the average transmittance is less than 70%, the sensitivity when used as an infrared ray shielding film is lowered. 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)

An average transmittance of 700 to 900 nm was calculated. When the average transmittance is 20% or more, the amount of noise increases when used as an infrared ray shielding film. 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 respect to the transmittance at a wavelength of 1200 nm, the transmittance is less than 15%, which indicates good infrared ray shielding in practical use. The transmittance at a wavelength of 1200 nm was evaluated according to the following criteria.

A: Less than 10%

B: 10% or more and less than 15%

C: 15% or more

(S / N ratio)

The ratio of the average transmittance S of the visible light region (430 to 580 nm) to the average transmittance N of the infrared region (700 to 900 nm) (S / N ratio) was taken and estimation was made on practical performance. The higher the S / N ratio, the better the performance. If the S / N ratio was 5 or higher, the S / N ratio was at the practical level and was judged to be usable. The S / N ratio was evaluated based on the following criteria.

A: 5 or more

B: Less than 5

(Visible light uniform transmittance)

X (visible light uniform transmittance) was determined based on the following formula from the average transmittance S of the visible light region (430 to 580 nm) and the minimum transmittance (S _min ) in the visible light region to evaluate the uniform transmittance of visible light .

_{X = ((SS min) /} S) × 100 (%)

It can be determined that the smaller X is, the higher the uniform transmittance 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, the infrared ray shielding films of Examples 1 to 3 are both excellent in visible light transmittance and infrared ray shielding property (A or B) and excellent in uniform transmittance of visible light. It is also understood that the infrared shielding films of Examples 1 to 3 can exhibit such good properties even though only one kind or two kinds of the organic pigment-containing paper are present.

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

Claims (14)

A phthalocyanine compound represented by the following formula (1)
By weight based on the total weight of the composition.

The plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X's are bonded to each other to form a bond, M is a hydrogen atom, a divalent metal atom, or a derivative of a metal atom of a trivalent or tetravalent metal, and n is, independently of each other, 3 to 6 carbon atoms, It is an integer.) 2. The composition according to claim 1, wherein the metal oxide, the copper compound (excluding the phthalocyanine compound)
Wherein the solid-state imaging device further comprises: 3. The composition for a solid-state image pickup device according to claim 2, wherein the infrared shielding agent is tungsten oxide. The composition for a solid-state image pickup device 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 based on the total solid content. The composition for a solid-state image pickup device according to any one of claims 1 to 4, wherein the content of the phthalocyanine compound is 0.1% by mass or more and 30% by mass or less based on the total solid content. The composition for a solid-state image pickup device according to any one of claims 1 to 5, wherein R in the formula (1) is a straight or branched alkyl group having 1 to 12 carbon atoms. 7. The method of claim 1, wherein M in the formula (1) is at least one element selected from the group consisting of H ₂ , Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , , VO, or TiO. 8. An infrared shielding film for a solid-state imaging element, comprising the composition for a solid-state imaging element according to any one of claims 1 to 7. 1. An infrared shielding film for a solid-state imaging device comprising substantially one or two kinds of organic pigments substantially satisfying the following (A) to (C).
(A) an average value of transmittance in a wavelength range of from 430 nm to 580 nm is 75% or more
(B) an average value of the transmittance in a wavelength range of 700 nm or more and 900 nm or less is 16.5% or less
(C) a transmittance at a wavelength of 1200 nm of not more than 10% The infrared ray shielding film according to claim 9, wherein (D) the infrared ray shielding film has a visible light transmittance of 10% or less.
(Average value of transmittance in a wavelength range of 430 nm to 580 nm - minimum value of transmittance in a wavelength range of 430 nm to 580 nm) / (average value of transmittance in a wavelength range of 430 nm to 580 nm) x 100 (%) 11. A composition according to any one of claims 9 to 10, characterized in that it comprises a metal oxide, a copper compound or a combination thereof,
Infrared ray shielding film. 12. The infrared shielding film according to claim 11, wherein the infrared shielding agent is tungsten oxide. 13. The infrared shielding film according to any one of claims 9 to 12, wherein the organic dye is a phthalocyanine compound represented by the following formula (1).

The plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X's are bonded to each other to form a bond, M is a hydrogen atom, a divalent metal atom, or a trivalent metal derivative, and the plurality of n's are each independently an integer of 3 to 6 .) A solid-state imaging device having the infrared shielding film according to any one of claims 8 to 13.

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