Composition for optical sensor

Abstract

A composition for optical sensors, comprising a phthalocyanine compound represented by the following formula (1) and a binder resin. In formula (1), each of R is independently an alkyl group with or without a substituent or an aryl group with or without a substituent. Each of X is independently a hydrogen atom, a halogen atom or an alkyl group. Xs can also be bonded to each other and form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, Pb, AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl2, SiBr2, SiI2, Si(OH)2, GeCl2, GeBr2, GeI2, SnCl2, SnBr2, SnI2, Sn(OH)2, TiO. Each of n is independently an integer of 3 to 6.

Description

[0001] This invention is a divisional application of the invention patent application filed on October 3, 2019, with application number 201980064495.5 (international application number PCT / JP2019 / 039121) entitled "Composition for Optical Sensors". Technical Field

[0002] This invention relates to a composition for optical sensors. Background Technology

[0003] Solid-state imaging elements, serving as optical sensors, are incorporated into video cameras, digital cameras, and mobile phones with camera functions. Specifically, known solid-state imaging elements include charge-coupled device (CCD) image sensors and complementary metal-oxide-semiconductor (CMOS) image sensors. The photodiodes in these solid-state imaging elements have sensitivity spanning from the visible light region to the infrared region. Therefore, filters for blocking infrared light are provided in solid-state imaging elements. By using these optical filters (infrared blocking filters), the sensitivity of the solid-state imaging element can be corrected in a manner approaching human visual acuity. Infrared blocking filters are sometimes also provided in optical sensors other than solid-state imaging elements.

[0004] The optical filter contains a pigment or dye that acts as an infrared shielding agent. The infrared shielding agent is required to have the properties of allowing sufficient visible light to pass through while absorbing infrared radiation. Phthalocyanine compounds have been investigated as one type of infrared shielding agent, particularly as a good shielding agent for near-infrared radiation (see Japanese Patent Application Publication Nos. 2008-201952).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2008-201952 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, in existing optical filters using phthalocyanine compounds, defects such as foreign matter can sometimes occur due to compatibility issues. These defects can sometimes affect the visible light transmittance or infrared shielding properties of the optical filter. Furthermore, when forming an infrared shielding film for an optical filter by coating a composition containing pigments such as phthalocyanine compounds, prolonged post-coating storage can easily lead to defects such as foreign matter in the resulting infrared shielding film. In the manufacturing process, it is desirable to obtain an infrared shielding film with minimal defects such as foreign matter, even after a period of hardening following coating.

[0010] Furthermore, existing optical filters do not adequately meet the requirements regarding visible light transmittance or infrared blocking properties. Specifically, when using optical filters as infrared blocking filters for optical sensors such as solid-state imaging elements, it is not only required that they have high visible light transmittance and low infrared transmittance, but also that the wavelength regions with high visible light transmittance and low infrared transmittance are wide, and that the wavelength regions with high visible light transmittance and low infrared transmittance are close to each other. If optical filters with these characteristics are used in optical sensors such as solid-state imaging elements, sensitivity, noise blocking function, and color reproduction can be improved.

[0011] The present invention was made in view of the above circumstances, and its object is to provide an optical sensor composition that can form an optical filter for an optical sensor with few defects such as foreign matter and good properties related to visible light transmittance and infrared shielding.

[0012] Technical means to solve the problem

[0013] The invention made to solve the aforementioned problem is a composition for an optical sensor, comprising a phthalocyanine compound represented by the following formula (1) and an adhesive resin.

[0014] [Chemistry 1]

[0015]

[0016] (In formula (1), each R is independently an alkyl group with or without a substituent, or an aryl group with or without a substituent. Each X is independently a hydrogen atom, a halogen atom, or an alkyl group. The X groups may also be bonded to each other and together with these bonded carbon chains to form an aromatic ring. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. Each n is independently an integer from 3 to 6.)

[0017] Another invention made to solve the aforementioned problem is a composition for an optical sensor containing a phthalocyanine compound represented by the following formula (2).

[0018] [Chemistry 2]

[0019]

[0020] (In formula (2), each R is independently an alkyl group with a substituent or an aryl group with a substituent. Each X is independently a hydrogen atom, a halogen atom, or an alkyl group. The multiple Xs may also be bonded to each other and form an aromatic ring together with these bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. Each n is independently an integer from 3 to 6)

[0021] The effects of the invention

[0022] According to the present invention, an optical sensor composition is provided, which can form an optical filter for an optical sensor with few defects such as foreign matter and good properties related to visible light transmittance and infrared shielding. Detailed Implementation

[0023] Hereinafter, a composition for an optical sensor according to an embodiment of the present invention will be described in detail.

[0024] <Composition for Optical Sensors (I)>

[0025] An optical sensor composition (I) according to one embodiment of the present invention (hereinafter also simply referred to as "composition (I)") contains [A1] phthalocyanine compound and [B] adhesive resin. Preferably, the composition further contains [C] infrared shielding agent, which is a metal oxide, a copper compound (excluding [A] phthalocyanine compound), or a combination thereof.

[0026] ([A1]phthalocyanine compounds)

[0027] [A1]phthalocyanine compounds are compounds represented by the following formula (1). [A1]phthalocyanine compounds have high transmittance in the visible light region (e.g., wavelengths above 430 nm and below 580 nm), and high shielding properties in the near-infrared region (e.g., wavelengths above 700 nm and below 800 nm). Furthermore, [A1]phthalocyanine compounds exhibit excellent compatibility with other components. The composition (I) contains the aforementioned [A1]phthalocyanine compound, thus enabling the formation of an optical filter with few defects such as foreign matter and excellent properties related to visible light transmittance and infrared shielding.

[0028] [Chemistry 3]

[0029]

[0030] In formula (1), each R is independently an alkyl group with or without a substituent, or an aryl group with or without a substituent. Each X is independently a hydrogen atom, a halogen atom, or an alkyl group. The X groups may also be bonded to each other and together with these bonded carbon chains to form an aromatic ring. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. Each n is independently an integer from 3 to 6.

[0031] Examples of alkyl groups represented by R include straight-chain or branched alkyl groups with 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, and tert-butyl. The upper limit for the number of carbon atoms in the alkyl group is preferably 12, more preferably 8, and even more preferably 4.

[0032] The aryl group represented by R can be a monovalent group consisting only of an aromatic ring, or a monovalent group formed by the bonding of an alkyl group to an aromatic ring. Specific examples of the aryl group represented by R include phenyl, tolyl, xylyl, naphthyl, anthracene, etc. The aryl group is preferably a group consisting only of an aromatic ring, more preferably phenyl or naphthyl, and phenyl is even more preferred in terms of visible light transmittance.

[0033] As for R, in terms of the heat resistance and other properties of the resulting optical filter, it is preferably an aryl group having a substituent or an unsubstituted group.

[0034] The alkyl and aryl groups represented by the plurality of Rs may or may not have substituents, but are preferably substituents. That is, the plurality of Rs are preferably independently alkyl groups or aryl groups with substituents. In this way, by having substituents in the plurality of Rs, the compatibility of [Al] phthalocyanine compounds is further improved, defects such as foreign matter in the resulting optical filter are further suppressed, and the properties related to visible light transmittance and infrared shielding are also improved. Furthermore, by having substituents in the plurality of Rs, the heat resistance of the resulting optical filter is also improved.

[0035] The substituents that the alkyl and aryl groups represented by the plurality of Rs can be alkenyl, alkynyl, or other hydrocarbon groups, but are preferably groups having heteroatoms. Heteroatoms refer to atoms other than hydrogen and carbon atoms. By including substituents with heteroatoms in the alkyl and aryl groups represented by the plurality of Rs, compatibility and other properties are further improved, defects such as foreign matter in the resulting optical filter are further suppressed, and properties related to visible light transmittance and infrared shielding are also improved. Furthermore, by including substituents with heteroatoms in the plurality of Rs, the heat resistance of the resulting optical filter is also improved. The heteroatoms are preferably halogen atoms, oxygen atoms, and sulfur atoms, and more preferably halogen atoms and oxygen atoms.

[0036] Examples of substituents with heteroatoms include: halogen atoms, alkoxy groups, alkylthio groups, cyano groups, nitro groups, carboxyl groups, hydroxyl groups, thiol groups, and amino groups.

[0037] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms, with fluorine atoms being the preferred choice.

[0038] Examples of alkoxy groups include methoxy, ethoxy, and propoxy, with methoxy and ethoxy being preferred, and methoxy being more preferred.

[0039] Examples of alkylthio groups include methylthio (CH3-S-), ethylthio (C2H5-S-), and propylthio (C3H7-S-), with methylthio and ethylthio being more preferred.

[0040] Among the substituents having heteroatoms, halogen atoms, alkoxy groups, and alkylthio groups are preferred, and halogen atoms and alkoxy groups are more preferred. Additionally, halogen atoms, methoxy groups, ethoxy groups, methylthio groups, ethylthio groups, or combinations thereof are also preferred.

[0041] The plurality of Rs may be the same or different, but are preferably the same.

[0042] As the halogen atom represented by X, the atoms exemplified as halogen atoms of the substituents can be listed.

[0043] As the alkyl group represented by X, examples can be given as the alkyl group represented by R.

[0044] The multiple X atoms can also be bonded to each other. Typically, among the multiple X atoms, two X atoms bonded to the same benzene ring bond to each other and together with these bonded carbon chains form an aromatic ring. Examples of the aromatic rings formed include benzene rings, naphthalene rings, and anthracene rings. The hydrogen atoms in these aromatic rings can also be substituted with hydrocarbon groups or other substituents.

[0045] The preferred form of X is a hydrogen atom. Furthermore, the plurality of X atoms may be the same or different, but are preferably the same.

[0046] Examples of divalent metal atoms represented by M include: Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, Pb, etc. Furthermore, a divalent metal atom refers to a metal atom that can become a divalent cation.

[0047] Here, the term "derivative of metal atoms" refers to a group of atoms containing metal atoms. The term "trivalent metal atom" refers to a metal atom that can become a trivalent cation. Examples of trivalent metal atoms include Al and In. The term "tetravalent metal atom" refers to a metal atom that can become a tetravalent cation. Examples of tetravalent metal atoms include Si, Ge, and Sn. Furthermore, metal atoms may also contain half-metal atoms. Examples of derivatives of the trivalent or tetravalent metal atoms represented by M include: AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl2, SiBr2, SiI2, Si(OH)2, GeCl2, GeBr2, GeI2, SnCl2, SnBr2, SnI2, Sn(OH)2, VO, TiO, etc.

[0048] The preferred form of M is H2 (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl2, AlCl, VO, and TiO, with VO being more preferred.

[0049] The lower limit of n is preferably 4. The upper limit of n is preferably 5, more preferably 4. Multiple n values ​​may be the same or different, but are preferably the same.

[0050] The lower limit of the maximum absorption wavelength of the [A1] 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, even more preferably 800 nm, and even more preferably 750 nm. By ensuring that the maximum absorption wavelength of the [A1] phthalocyanine compound is within the aforementioned range, optical filters with better properties related to visible light transmittance and infrared shielding can be formed.

[0051] [A1] There are no particular limitations on the synthesis of phthalocyanine compounds; known methods can be combined to synthesize them. For example, they can be synthesized by reacting phthalonitrile compounds represented by formula (i) or 1,3-diiminoisoindoline compounds represented by formula (ii) with a metal or a metal derivative.

[0052] [Chemistry 4]

[0053]

[0054]

[0055] In equations (i) and (ii), R, X and n have the same meaning as in equation (1).

[0056] Examples of metals or metal derivatives include: Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, and their halides, carboxylates, sulfates, nitrates, carbonyl compounds, oxides, complexes, etc. Among these, metal halides and carboxylates are particularly preferred. Examples of these include: copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, ferric chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxychloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride, etc.

[0057] The reaction temperature is, for example, 60°C to 300°C, preferably 100°C to 220°C. The reaction time is, for example, 30 minutes to 72 hours, preferably 1 hour to 48 hours. A solvent is preferably used in the reaction. The solvent used in the reaction is preferably an organic solvent with a boiling point of 60°C or higher, more preferably an organic solvent with a boiling point of 80°C or higher.

[0058] Examples of organic solvents used include: methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, 1-heptanol, 1-octanol, 1-dodecanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylethanol, diethylethanol, etc., as well as high-boiling-point solvents such as dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, 1,3-dimethyl-2-imidazolidinone (DMI), and urea.

[0059] The reaction can be carried out in the presence or absence of a catalyst, but preferably in the presence of a catalyst. As a catalyst, inorganic catalysts such as ammonium molybdate or basic organic catalysts such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) can be used.

[0060] In the case where M in formula (1) is a phthalocyanine compound with two hydrogen atoms, it can be manufactured by reacting a phthalonitrile compound represented by formula (i) or a 1,3-diiminoisoindoline compound represented by formula (ii) with metallic sodium or metallic potassium under the stated reaction conditions, followed by removing sodium or potassium as the central metal by hydrochloric acid, sulfuric acid, or the like.

[0061] After the reaction is complete, the solvent is removed by distillation, or the reaction solution is discharged into a less suitable solvent for the phthalocyanine compound to precipitate the target compound. The precipitate is then filtered to obtain the phthalocyanine compound represented by formula (1). If necessary, the target compound can be further purified using known purification methods such as recrystallization or column chromatography to obtain a higher purity.

[0062] Furthermore, the phthalonitrile compounds represented by formula (i) and the 1,3-diiminoisoindoline compounds represented by formula (ii) can be synthesized by known methods. For example, the method described in Japanese Patent Application Publication No. 2003-516421 can be used for synthesis.

[0063] The lower limit of the content of the [Al] phthalocyanine compound in the total solid components (all components other than the solvent) of the composition (I) is preferably 0.1% by mass, more preferably 0.5% by mass, and even more preferably 1% by mass, and even more preferably 2% 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, and even more preferably 8% by mass. By setting the content of the [Al] phthalocyanine compound within the above range, the properties related to the visible light transmittance and infrared shielding of the resulting optical filter become better.

[0064] [A1] Phthalocyanine compounds can be used alone or in combination of two or more.

[0065] ([B] Adhesive resin)

[0066] [B] The adhesive resin is a component that retains [A1] phthalocyanine compounds and the like in the resulting optical filter and serves as a matrix.

[0067] To improve strength, sensitivity, heat resistance, etc., the [B] adhesive resin preferably has a polymerizable group, more preferably has a structural unit containing a polymerizable group. Examples of polymerizable groups include: oxetyl, oxetyl, (meth)acryloyl, vinyl, alkoxysilyl, etc., preferably oxetyl, oxetyl, (meth)acryloyl, alkoxysilyl, or a combination thereof, more preferably (meth)acryloyl.

[0068] Examples of monodimers providing structural units containing polymerizable groups include: glycidyl (meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexyl methyl (meth)acrylate, and 3,4-epoxytricyclo (meth)acrylate [5.2.1.0]. 2.6 ] Decyl ester, 3-methacryloyloxypropyltriethoxysilane, etc.

[0069] Alternatively, for example, structural units containing polymerizable groups can be introduced by reacting a compound having polymerizable groups such as carboxyl groups (oxetyl, oxetyl, etc.) and (meth)acryloyl groups with a resin containing structural units having carboxyl groups.

[0070] The lower limit of the content of the structural unit with polymerizable groups in the [B] adhesive resin is 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, and sometimes even more preferably 30% by mass, 50% by mass, or 75% by mass, relative to 100% by mass of the [B] adhesive resin. On the other hand, the upper limit of the content is preferably 95% by mass, more preferably 90% by mass, and even more preferably 85% by mass.

[0071] To improve heat resistance, the [B] adhesive resin preferably has a ring structure in its main chain. The number of ring elements in the ring structure can be, for example, 3 to 12, but is preferably 5 to 8.

[0072] Examples of monomers that provide structural units with a ring structure in the main chain include N-substituted maleimide monomers and cycloolefins.

[0073] The term "N-substituted maleimide monomer" refers to a compound in which the hydrogen atom on the nitrogen atom bonded to the maleimide is replaced by a substituent. The substituent is preferably a hydrocarbon group, more preferably a hydrocarbon group having a cyclic structure, and even more preferably an aromatic hydrocarbon group. Examples of N-substituted maleimide monomers include: N-phenylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, and N-methylmaleimide.

[0074] Examples of cyclic alkenes include norbornene alkenes, tetracyclododecene alkenes, and dicyclopentadiene alkenes.

[0075] In addition, phenolic resins and the like can also be used as adhesive resins with a ring structure in the main chain.

[0076] The content of structural units having a ring structure in the main chain in the [B] adhesive resin, relative to 100% by mass, is preferably 1% to 50% by mass, more preferably 5% to 30% by mass.

[0077] [B] The adhesive resin preferably contains acidic groups. Examples of acidic groups include carboxyl groups, anhydride groups, phenolic hydroxyl groups, and sulfonyl groups. Among these, carboxyl groups are preferred as acidic groups. [B] The adhesive resin is preferably a resin containing structural units having one or more acidic groups. When the [B] adhesive resin has acidic groups, it exhibits good alkali solubility. When the [B] adhesive resin is alkali-soluble, alkali development can be performed, and optical filters with desired pattern shapes can be formed.

[0078] As a monomer providing structural units containing acidic groups, monomers containing carboxyl groups include, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, butenoic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesocarboxylic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as succinate mono[2-(meth)acryloyloxyethyl] ester and phthalate mono[2-(meth)acryloyloxyethyl] ester; and mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxylated polycaprolactone mono(meth)acrylate.

[0079] Examples of monoisopropylforms containing phenolic hydroxyl groups include: 4-vinylphenol, 4-isopropenylphenol, and 4-hydroxyphenyl (meth)acrylate.

[0080] The content of the structural unit containing the acid group in the [B] adhesive resin is preferably 1% to 50% by mass, more preferably 5% to 30% by mass, relative to 100% by mass of the [B] adhesive resin.

[0081] [B] The adhesive resin may further comprise other structural units. Examples of such units providing other structural units include:

[0082] Styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthene and other aromatic vinyl compounds,

[0083] Methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl methacrylate, isobornyl methacrylate, tricyclo[5.2.1.0] 2,6Decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glyceryl mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc. (meth)acrylates, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0] 2,6 Vinyl ethers such as decane-8-yl vinyl ether, pentacyclic pentadecyl vinyl ether, and 3-(ethoxymethyl)-3-ethyloxetane.

[0084] Polystyrene, poly(meth)acrylate, poly(meth)acrylate-n-butyl acrylate, polysiloxane, and other macromonomers with mono(meth)acryloyl groups at the ends of their polymer chains.

[0085] [B] The adhesive resin can be obtained by polymerizing the aforementioned monomers using known methods. Furthermore, [B] the adhesive resin can be used alone or in combination with two or more other resins.

[0086] [B]The polystyrene-converted weight-average molecular weight (Mw) of the adhesive resin, as determined by gel permeation chromatography (GPC), is preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and even more preferably 4,000 to 30,000. If Mw is within this range, an [B] adhesive resin with excellent solubility relative to the solvent or developer and sufficient mechanical properties can be obtained.

[0087] The lower limit of the content of the [B] adhesive resin in the total solid components of the composition (I) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass. On the other hand, the upper limit of the content is preferably 70% by mass, more preferably 60% by mass, and even more preferably 50% by mass. By setting the content of the [B] adhesive resin within the above range, the properties related to the visible light transmittance and infrared shielding of the resulting optical filter can be fully utilized, and heat resistance and other properties can also be improved.

[0088] ([C] Infrared shielding agent)

[0089] The [C] infrared shielding agent is a metal oxide, a copper compound (except for [Al] phthalocyanine compounds), or a combination thereof. Preferably, the [C] infrared shielding agent is a compound having a very high absorption wavelength in the range of 800 nm to 2000 nm. By using the [C] infrared shielding agent in combination with an [Al] phthalocyanine compound, the infrared shielding performance of the resulting optical filter is further improved.

[0090] Metal oxides that can be used as [C] infrared shielding agents include, for example, tungsten oxide compounds, quartz (SiO2), magnetite (Fe3O4), aluminum oxide (Al2O3), titanium dioxide (TiO2), zirconium oxide (ZrO2), spinel (MgAl2O4), etc.

[0091] Regarding copper compounds used as [C] infrared shielding agents, examples include copper phthalocyanine compounds and other copper complexes. Examples of copper phthalocyanine compounds include copper phthalocyanine, copper chloride phthalocyanine, copper bromide phthalocyanine chloride, and copper bromide phthalocyanine.

[0092] As the infrared shielding agent [C], a metal oxide is preferred, and a tungsten oxide-based compound is more preferred. Tungsten oxide-based compounds are infrared shielding agents with high absorption of infrared light (especially infrared light with wavelengths of about 800 nm and below 1200 nm) (i.e., high infrared shielding performance) and low absorption of visible light. Therefore, by including a tungsten oxide-based compound in the composition (I), good visible light transmittance of the resulting optical filter can be maintained while improving infrared shielding performance. The infrared shielding agent [C] can be used alone or in combination of two or more.

[0093] As a tungsten oxide compound, the tungsten oxide compound represented by the following formula (3) is more preferred.

[0094] A x WO y ···(3)

[0095] In equation (3), A is a metallic element. 0.001≦x≦1.1. 2.2≦y≦3.0.

[0096] Examples of metallic elements represented by A in formula (3) include: alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, etc. A may represent one or more metallic elements.

[0097] The metal A is preferably an alkali metal, more preferably Rb and Cs, and even more preferably Cs. That is, the metal oxide is more preferably cesium tungsten oxide.

[0098] By ensuring that x in equation (3) is 0.001 or higher, infrared radiation can be sufficiently blocked. The lower limit of x is preferably 0.01, and more preferably 0.1. On the other hand, by ensuring that x is 1.1 or lower, the formation of impurity phases in tungsten oxide compounds can be more reliably avoided. The upper limit of x is preferably 1, and more preferably 0.5.

[0099] By having y = 2.2 or higher in equation (3), the chemical stability of the material can be further improved. The lower limit of y is preferably 2.5. On the other hand, by having y = 3.0 or lower, infrared radiation can be sufficiently blocked.

[0100] As a specific example of the tungsten oxide compounds represented by formula (3), Cs can be cited. 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 WO3, etc., preferably Cs 0.33 WO3 and Rb 0.33 WO3, and therefore preferably Cs 0.33 WO3.

[0101] The [C] infrared masking agent is preferably a microparticle. The upper limit of the average particle size (D50) of the [C] infrared masking agent is preferably 500 nm, more preferably 200 nm, further preferably 50 nm, and even more preferably 30 nm. By having an average particle size below this upper limit, visible light transmittance can be further improved. On the other hand, for reasons such as ease of handling during manufacturing, the average particle size of the [C] infrared masking agent is typically 1 nm or more, and may also be 10 nm or more.

[0102] [C] Infrared shielding agents can also be synthesized by known methods and are available as commercially available products. In the case of metal oxides, such as tungsten oxide compounds, tungsten oxide compounds can be obtained, for example, by heat treatment of tungsten compounds in an inert gas environment or a reducing gas environment. Alternatively, tungsten oxide compounds can also be obtained, for example, as dispersions of tungsten microparticles such as Sumitomo Metal Mining's "YMF-02".

[0103] The lower limit of the content of the [C] infrared shielding agent in the total solid components of the composition (I) is preferably 1% by mass, more preferably 5% by mass, and even more preferably 10% by mass, and even more preferably 15% by mass. On the other hand, the upper limit of the content is preferably 70% by mass, more preferably 50% by mass, and even more preferably 40% by mass, and even more preferably 30% by mass. By setting the content of the [C] infrared shielding agent within the above range, the properties related to the visible light transmittance and infrared shielding of the resulting optical filter become better.

[0104] The lower limit of the mass ratio ([C] / [Al]) of the content of the [C] infrared shielding agent to the content of the [Al] phthalocyanine compound is preferably 1, more preferably 2, and even more preferably 3. On the other hand, the upper limit of the mass ratio ([C] / [Al]) is preferably 40, more preferably 20, and even more preferably 10. By setting the content ratio of the [Al] phthalocyanine compound to the [C] infrared shielding agent within the aforementioned range, the properties related to the visible light transmittance and infrared shielding of the resulting optical filter become better.

[0105] ([D] dispersant)

[0106] The composition (I) preferably further comprises a [D] dispersant. The [D] dispersant improves the uniform dispersion of the [C] infrared shielding agent (especially the metal oxide), resulting in better properties related to the visible light transmittance and infrared shielding of the resulting optical filter.

[0107] Examples of [D] dispersants include: urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, and (meth)acrylic acid dispersants. Among these, (meth)acrylic acid dispersants are preferred. The [D] dispersant is preferably a block copolymer.

[0108] [D] Dispersants are commercially available. Examples of (meth)acrylic acid dispersants include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, and BYK-LPN22102 (all manufactured by BYK Chemicals). Examples of carbamate dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, and Disperbyk-170. Disperbyk-182 and Disperbyk-2164 (both manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol), polyimide dispersants include Solsperse 24000 (manufactured by Lubrizol), polyester dispersants include Ajisper PB821, Ajisper PB822, Ajisper PB880, and Ajisper PB881 (manufactured by Ajinomoto Fine-Techno), and BYK-LPN21324 (manufactured by BYK).

[0109] The lower limit of the amine value of the [D] dispersant is preferably 10 mg KOH / g, more preferably 40 mg KOH / g, and even more preferably 80 mg KOH / g. On the other hand, the upper limit of the amine value is preferably 300 mg KOH / g, more preferably 200 mg KOH / g, and even more preferably 160 mg KOH / g. By using a dispersant with the aforementioned amine value, the dispersibility of the [C] infrared shielding agent is improved, and the characteristics of the resulting optical filter can be further improved. Furthermore, the term "amine value" refers to the number of mg of KOH equivalent to the HCl required to neutralize 1 g of the solid component of the dispersant.

[0110] The lower limit of the content of the [D] dispersant relative to 100 parts by weight of the [C] infrared shielding agent is preferably 5 parts by weight, more preferably 10 parts by weight, and even more preferably 20 parts by weight. On the other hand, the upper limit of the content is preferably 200 parts by weight, more preferably 100 parts by weight, and even more preferably 60 parts by weight.

[0111] ([E] Polymerizing compounds)

[0112] The composition (I) preferably further comprises an [E] polymerizable compound. When the composition (I) contains an [E] polymerizable compound, it exhibits good curability or good heat resistance in the resulting optical filter. An [E] polymerizable compound refers to a compound having two or more polymerizable groups. Furthermore, [B] adhesive resins having two or more polymerizable groups are not included in the [E] polymerizable compound. Examples of polymerizable groups include vinyl unsaturated groups, oxetyl, oxetyl, and N-alkoxymethylamino groups. As the [E] polymerizable compound, compounds having two or more (meth)acryloyl groups and compounds having two or more N-alkoxymethylamino groups are preferred, and compounds having two or more (meth)acryloyl groups are more preferred. One or more [E] polymerizable compounds may be used.

[0113] Examples of compounds having two or more (meth)acryloyl groups include: polyfunctional (meth)acrylates as reactants of aliphatic polyhydroxy compounds with (meth)acrylic acid, polyfunctional (meth)acrylates modified with caprolactone, polyfunctional (meth)acrylates modified with epoxide, polyfunctional urethane (meth)acrylates as reactants of hydroxyl-containing (meth)acrylates with polyfunctional isocyanates, and polyfunctional (meth)acrylates with carboxyl groups as reactants of hydroxyl-containing (meth)acrylates with acid anhydrides.

[0114] Here, examples of the aliphatic polyhydroxy compounds include, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, or trivalent or higher aliphatic polyhydroxy compounds such as glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the (meth)acrylates containing hydroxyl groups include, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanates include, for example, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of such acid anhydrides include: succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and other dicarboxylic acid anhydrides, or pyromellitic dianhydride, biphenyl tetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, and other tetracarboxylic acid dianhydrides.

[0115] Specific examples of compounds having two or more (meth)acryloyl groups include: ω-carboxylated polycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate, dihydroxymethyltricyclodecane di(meth)acrylate, and 2-hydroxymethyl methacrylate. 3-(meth)acryloyloxypropyl ester, 2-(2'-ethyleneoxyethoxy)ethyl acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, carbamate (meth)acrylate compounds, etc.

[0116] Among compounds having two or more (meth)acryloyl groups, polyfunctional (meth)acrylates are preferred, and more preferably polyfunctional (meth)acrylates having three or more but less than ten (meth)acryloyl groups. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred.

[0117] Compounds having two or more N-alkoxymethyl amino groups include, for example, compounds with melamine, benzoguanamine, or urea structures. Specific examples of compounds having two or more N-alkoxymethyl amino groups include: N,N,N',N',N”,N”-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycourea.

[0118] As a lower limit for the content of the [E] polymeric compound in the total solid components of the composition (I), it is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass. On the other hand, as an upper limit for the content, it is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass.

[0119] ([F] Polymerization initiator)

[0120] The composition (I) preferably contains a [F] polymerization initiator. Examples of [F] polymerization initiators include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. This imparts photosensitivity (radiosensitivity) to the composition (I). A photopolymerization initiator is a compound that generates an active species that initiates the polymerization of [E] polymerizable compounds upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. One or more [F] polymerization initiators may be used.

[0121] Examples of [F] polymerization initiators include: thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, and imide sulfonate compounds. Among these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds are preferred, and O-acyloxime compounds are more preferred.

[0122] Examples of thioxanthone compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0123] Examples of acetophenone compounds include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1-one, etc.

[0124] Examples of biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0125] Furthermore, when using biimidazole compounds, it is preferable to use a hydrogen donor in conjunction with the compound to improve sensitivity. The term "hydrogen donor" here refers to a compound that can supply hydrogen atoms to free radicals generated by the biimidazole compound through exposure. Examples of hydrogen donors include thiol-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

[0126] Examples of triazine compounds include those described in paragraphs

[0063] to

[0065] of Japanese Patent Publication No. 57-6096 and Japanese Patent Application Publication No. 2003-238898.

[0127] Examples of O-acyl oxime compounds include: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), acetone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), acetone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxanepentyl)methoxybenzoyl}-9H-carbazole-3-yl]-1-(O-acetyl oxime), etc. Commercially available O-acyloxime compounds include NCI-831, NCI-930 (manufactured by ADEKA Corporation), OXE-03, and OXE-04 (manufactured by BASF Corporation).

[0128] When using a photopolymerization initiator, a sensitizer may also be used in conjunction. Examples of such sensitizers include: 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

[0129] The lower limit of the content of the [F] polymerization initiator in the total solid components of the composition (I) is preferably 1% by mass, more preferably 3% by mass. On the other hand, the upper limit of the content is preferably 30% by mass, more preferably 10% by mass.

[0130] (Other organic pigments)

[0131] The composition (I) may also contain known organic pigments other than [A1] phthalocyanine compounds and organic pigments other than copper compounds that serve as [B] infrared shielding agents. Examples of other organic pigments include diimine compounds, squaric acid lactonium salt compounds, anthocyanin compounds, naphthalene phthalocyanine compounds, quarteriene compounds, ammonium compounds, imine compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxacyanine compounds, ketone-onium compounds, and hexaphyrin compounds (except those containing copper atoms). Furthermore, phthalocyanine compounds other than [A1] phthalocyanine compounds and phthalocyanine compounds that serve as [B] infrared shielding agents may also be used.

[0132] Furthermore, it is preferable to use a [A1] phthalocyanine compound in combination with a phthalocyanine compound other than [A1] 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. On the other hand, the upper limit of the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 900 nm, more preferably 850 nm, sometimes even more preferably 800 nm, and sometimes even more preferably 750 nm. The lower limit of the difference between the maximum absorption wavelength of the [A1] phthalocyanine compound and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm. On the other hand, the upper limit of the difference is preferably 100 nm, more preferably 80 nm, and even more preferably 60 nm. Various phthalocyanine compounds known in the art can be cited as examples of [a] phthalocyanine compounds.

[0133] The lower limit of the content of the [Al] phthalocyanine compound in all organic pigments in the composition (I) is preferably 50% by mass, more preferably 70% by mass, sometimes even more preferably 80% by mass, sometimes even more preferably 90% by mass, and sometimes even more preferably 99% by mass. The composition (I) is sometimes preferably composed of substantially only the [Al] phthalocyanine compound. By reducing the content of other organic pigments in the manner described, the productivity of the composition (I) can be improved.

[0134] (additive)

[0135] In addition to the [A1] to [F] components and other organic pigments, the composition (I) may also contain various additives as needed.

[0136] Examples of additives include: surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, residue improvers, developer properties improvers, and reaction modifiers.

[0137] Examples of surfactants include fluorosurfactants and silicone surfactants.

[0138] Examples of adhesion promoters include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0139] Examples of antioxidants include: 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The content of these antioxidants is typically set to 0.01 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the [A]phthalocyanine compound.

[0140] Examples of UV absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones.

[0141] Sodium polyacrylate can be listed as an anti-coagulant.

[0142] Examples of residue improvers include: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, medoconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol.

[0143] Examples of agents that improve developability include: mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, ω-carboxylated polycaprolactone mono(meth)acrylate, etc.

[0144] Examples of reaction modifiers include polyfunctional thiols.

[0145] The lower limit of the content of the ingredients other than [A1] to [F] and other organic pigments in the total solid components of the composition (I) is preferably 0.1% by mass, more preferably 1% by mass. On the other hand, the upper limit of the content is preferably 10% by mass, more preferably 5% by mass.

[0146] (solvent)

[0147] The composition (I) is typically prepared as a liquid composition containing a solvent (dispersion medium). The solvent may be suitably selected as long as it disperses or dissolves other components without reacting with them and has moderate volatility.

[0148] Examples of solvents include:

[0149] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, 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.

[0150] Methyl lactate, ethyl lactate, and other alkyl lactate esters

[0151] Methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol, and other cycloalkyl alcohols.

[0152] Ketone alcohols such as diacetone alcohol

[0153] 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, dipropylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and other (poly)alkylene glycol monoalkyl ether acetates.

[0154] Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers,

[0155] Ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, cyclic ketones such as cyclopentanone, cyclohexanone, etc.

[0156] Diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0157] Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, 3-methyl-3-methoxybutylpropionate, and other alkoxycarboxylic acid esters.

[0158] Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, and other esters.

[0159] Aromatic hydrocarbons such as toluene and xylene

[0160] Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0161] The content of solvent in the composition (I) is not particularly limited. The lower limit of the concentration of solid components (the total concentration of all components other than the solvent) in the composition (I) is preferably 5% by mass, more preferably 10% by mass. On the other hand, the upper limit of the concentration of solid components is preferably 50% by mass, more preferably 40% by mass. By setting the concentration of solid components within the aforementioned range, dispersibility, stability, coatability, etc., become better.

[0162] (Preparation method)

[0163] There is no particular limitation on the preparation method of the composition (I), and it can be prepared by mixing the components. For example, if the composition contains a metal oxide as an infrared shielding agent (C) and a dispersant (D), the following method can be used: first, a dispersion containing the infrared shielding agent (C), the dispersant (D), and a solvent is prepared; then, an phthalocyanine compound (A1), a binder resin (B), and other components as needed are added to the dispersion and mixed. The dispersion or the composition (I) may also be filtered as needed to remove agglomerates.

[0164] <Composition for Optical Sensors (II)>

[0165] An optical sensor composition (II) according to one embodiment of the present invention (hereinafter also simply referred to as "composition (II)") contains a [A2] phthalocyanine compound. The [A2] phthalocyanine compound is a compound represented by the following formula (2). Since composition (II) contains the [A2] phthalocyanine compound, it can form an optical filter with few defects such as foreign matter and good properties related to visible light transmittance and infrared shielding.

[0166] [Chemistry 5]

[0167]

[0168] In formula (2), each R is independently an alkyl group with a substituent or an aryl group with a substituent. Each X is independently a hydrogen atom, a halogen atom, or an alkyl group. The X groups may also be bonded to each other and form an aromatic ring together with the bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. Each n is independently an integer from 3 to 6.

[0169] Regarding the [A2] phthalocyanine compound, it is the same as the [A1] phthalocyanine compound, except that each of the plurality of Rs is independently an alkyl group with a substituent or an aryl group with a substituent. The preferred form of the [A2] phthalocyanine compound is also the same as that of the [A1] phthalocyanine compound.

[0170] The composition (II) is identical to the composition (I) except that it contains [A2] phthalocyanine compound instead of [A1] phthalocyanine compound and does not make [B] adhesive resin an essential component. The composition (II) preferably contains [B] adhesive resin. Otherwise, the specific form and preferred form of the composition (II) are the same as those of the composition (I).

[0171] <Infrared shielding film>

[0172] An infrared shielding film for optical filters can be formed from the composition (I) and composition (II) of one embodiment of the present invention (hereinafter, composition (I) and composition (II) are collectively referred to as "the composition"). The infrared shielding film has few defects such as foreign matter and has good properties related to visible light transmittance and infrared shielding.

[0173] The infrared shielding film can be formed, for example, by the following method. First, after coating the composition onto a support, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Then, after exposing the coating film, development is performed using a developer, and the unexposed portions of the coating film are dissolved and removed. Subsequently, by post-baking, an infrared shielding film (I) patterned into a predetermined shape can be obtained. Furthermore, if the composition does not contain [E] polymerizable compounds and [F] polymerization initiators, curing treatments such as exposure may not be necessary. Alternatively, development treatment may be omitted, in which case an unpatterned infrared shielding film can be formed.

[0174] The transparent substrate, microlens, color filter, etc., are suitable as the support for coating the composition. The coating can be performed using suitable coating methods such as spray coating, roller coating, spin coating, slit coating, and bar coating.

[0175] The heating and drying conditions for the pre-baking process are, for example, 70°C or higher and 110°C or lower, for 1 minute or more and 10 minutes or less.

[0176] Examples of radiation sources used for coating exposure include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps; and laser sources such as argon ion lasers, yttrium aluminum garnet (YAG) lasers, XeCl excimer lasers, and nitrogen lasers. Ultraviolet light-emitting diodes (LEDs) can also be used as exposure sources. The preferred wavelength is radiation in the range of 190 nm to 450 nm. The radiation exposure dose is typically 10 J / m². 2 Above 50,000 J / m 2 Below, left and right.

[0177] The developing solution is typically an alkaline developing solution. Examples of preferred alkaline developing solutions include aqueous solutions of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene. Appropriate amounts of water-soluble organic solvents such as methanol and ethanol, or surfactants, may also be added to the alkaline developing solution. Furthermore, a water wash is typically performed after development.

[0178] As a developing process, various methods can be applied, including spray developing, mist developing, dip developing, and puddle developing. The developing conditions are approximately 5 seconds to 300 seconds at room temperature.

[0179] The conditions for post-baking are typically between 180°C and 280°C, and between 1 minute and 60 minutes.

[0180] The lower limit for the average film thickness of the infrared shielding film formed in the manner described above is typically 0.5 μm, preferably 1 μm. On the other hand, the upper limit for the average film thickness is typically 10 μm, preferably 5 μm. When the average film thickness of the infrared shielding film is within the aforementioned range, the balance between visible light transmittance and infrared shielding becomes better.

[0181] <Optical Filters>

[0182] An infrared shielding film formed from the composition of one embodiment of the present invention can be used in optical filters. Optical filters having the infrared shielding film have fewer defects such as foreign matter and possess excellent properties related to visible light transmittance and infrared shielding. The optical filter is used as an optical filter for optical sensors such as solid-state imaging elements.

[0183] The optical filter may be an optical filter containing only the infrared shielding film, or it may be an optical filter containing the infrared shielding film and other constituent components. For example, the optical filter may also be a laminate having the infrared shielding film and other layers.

[0184] The infrared shielding film is preferably incorporated as a component into an optical sensor such as a solid-state imaging element. In this case, the infrared shielding film functions as an optical filter (infrared cut-off filter) in the form of a single unit. Incorporating the infrared shielding film into the optical sensor is preferred because it provides greater process margin. When the infrared shielding film is incorporated into a solid-state imaging element, it can be disposed, for example, on the outer surface of a microlens of the solid-state imaging element, between a microlens and a color filter, or between a color filter and a photodiode. The infrared shielding film is preferably stacked between a microlens and a color filter or between a color filter and a photodiode.

[0185] The optical filter can also be an optical filter formed by laminating the infrared blocking film onto the surface of a transparent substrate. The transparent substrate can be glass or a transparent resin. Examples of transparent resins include polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide. The optical filter is also preferably used as an infrared cut-off filter in a solid-state imaging element.

[0186] Optical sensors, such as solid-state imaging elements equipped with the aforementioned optical filters, are useful in digital still cameras, mobile phone cameras, digital video cameras, personal computer (PC) cameras, surveillance cameras, automotive cameras, portable information terminals, computers, game consoles, medical devices, and the like.

[0187] <Optical Sensors>

[0188] The optical filter is used in optical sensors such as solid-state imaging elements. The optical filter has few defects such as foreign objects and possesses excellent properties related to visible light transmittance and infrared shielding. Therefore, optical sensors such as solid-state imaging elements using the optical filter exhibit high sensitivity, color reproduction, and other properties, and are highly practical.

[0189] The following description uses a solid-state imaging element as an example of an optical sensor. This solid-state imaging element typically has a structure in which layers containing multiple photodiodes, color filters, and microlenses are stacked sequentially. Additionally, a planarization layer may be provided between these layers. Light is incident on the microlens side of the solid-state imaging element. The incident light passes through the microlens and color filters to reach the photodiodes. Furthermore, regarding the color filters, for example, each of the R (red), G (green), and B (blue) filters is configured such that only light within a specific wavelength range can pass through.

[0190] In the solid-state imaging element, the optical filter (infrared shielding film) can be disposed on the outer surface of the microlens, between the microlens and the color filter, or between the color filter and the layer on which multiple photodiodes are disposed. Preferably, the optical filter is stacked between the microlens and the color filter, or between the color filter and the photodiodes. Furthermore, other layers (such as planarization layers) can also be further disposed between the optical filter and the microlens, color filter, photodiodes, etc.

[0191] Specific examples of the solid-state imaging element include CCD or CMOS sensors used in camera modules. This solid-state imaging element is useful in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, portable information terminals, computers, game consoles, medical devices, and the like.

[0192] Example

[0193] The present invention will now be described in detail based on embodiments, but the present invention is not limited to these embodiments.

[0194] <Synthetic Example 1> Synthesis of Phthalocyanine Compound (a-1)

[0195] 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline, 4.76 g of vanadium trichloride, and 13.74 g of DBU were added to 100 mL of 1-pentanol and stirred at an internal temperature of 125 °C for 24 hours. Then, 600 mL of methanol was added, the precipitate was filtered off, and dried. Purification by column chromatography (silica gel / toluene) yielded 11.2 g of a green powder. The obtained compound was confirmed as the target compound represented by formula (a-1) based on the following analytical results.

[0196] MS: (EI)m / z 2245M +

[0197] • Elemental analysis values: Measured values ​​(C: 68.44%, H: 6.44%, N: 4.99%);

[0198] Theoretical values ​​(C: 68.47%, H: 6.46%, N: 4.99%)

[0199] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 734.5 nm, with a gamma of 6.75 × 10⁻⁶. 4 mL / g·cm.

[0200] [Chemistry 6]

[0201]

[0202] Furthermore, in the formula, "*" represents a bond (the same applies to the following chemical formulas).

[0203] <Synthetic Example 2> Synthesis of Phthalocyanine Compound (a-2)

[0204] Except that 18.6 g of 4,7-bis(4-methoxybutyl)-1,3-diiminobenzisisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline in Synthesis Example 1, 14.5 g of green powder was obtained in the same manner as in Synthesis Example 1. The obtained compound was confirmed to be the compound (a-2) represented by the following formula (a-2) as the target compound based on the analytical results described below.

[0205] MS: (EI) m / z 1267M +

[0206] • Elemental analysis values: Measured values ​​(C: 68.20%, H: 7.66%, N: 8.82%);

[0207] Theoretical values ​​(C: 68.17%, H: 7.63%, N: 8.83%)

[0208] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 734.0 nm, with a gamma of 1.21 × 10⁻⁶. 5 mL / g·cm.

[0209] [Chemistry 7]

[0210]

[0211] <Synthetic Example 3> Synthesis of Phthalocyanine Compound (a-3)

[0212] Except that 29.4 g of 4,7-bis(4-(3-methoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline in Synthesis Example 1, 5.9 g of green powder was obtained in the same manner as in Synthesis Example 1. The obtained compound was confirmed to be the compound represented by the following formula (a-3) as the target compound based on the analytical results described below.

[0213] MS: (EI)m / z 2003M +

[0214] • Elemental analysis values: Measured values ​​(C: 71.85%, H: 6.44%, N: 5.57%);

[0215] Theoretical values ​​(C: 71.87%, H: 6.43%, N: 5.59%)

[0216] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 735.5 nm, with a gamma of 7.40 × 10⁻⁶. 4 mL / g·cm.

[0217] [Chemistry 8]

[0218]

[0219] <Synthetic Example 4> Synthesis of Phthalocyanine Compound (a-4)

[0220] Except that 28.0 g of 4,7-bis(4-(2-fluorophenoxy)butyl)-1,3-diiminobenzisisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline in Synthesis Example 1, 11.2 g of green powder was obtained in the same manner as in Synthesis Example 1. The obtained compound was confirmed to be the compound (a-4) represented by the following formula (a-4) as the target compound based on the analytical results described below.

[0221] MS: (EI)m / z 1908M +

[0222] • Elemental analysis values: Measured values ​​(C: 70.49%, H: 5.51%, N: 5.85%);

[0223] Theoretical values ​​(C: 70.47%, H: 5.49%, N: 5.87%)

[0224] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 735.5 nm, with a gamma of 7.89 × 10⁻⁶. 4 mL / g·cm.

[0225] [Chemistry 9]

[0226]

[0227] <Synthetic Example 5> Synthesis of Phthalocyanine Compound (a-5)

[0228] Except that 38.8 g of 4,7-bis(4-((1,6-dimethoxynaphthyl-2-yl)oxy)butyl)-1,3-diiminobenzisisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline in Synthesis Example 1, 31.0 g of green powder was obtained in the same manner as in Synthesis Example 1. The obtained compound was confirmed to be the compound represented by the following formula (a-5) as the target compound based on the analytical results described below.

[0229] MS: (EI)m / z 2645M +

[0230] • Elemental analysis values: Measured values ​​(C: 72.62%, H: 6.05%, N: 4.30%);

[0231] Theoretical values ​​(C: 72.63%, H: 6.10%, N: 4.23%)

[0232] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 735.5 nm, with a gamma of 5.85 × 10⁻⁶. 4 mL / g·cm.

[0233] [Chemistry 10]

[0234]

[0235] <Synthetic Example 6> Synthesis of Phthalocyanine Compound (a-6)

[0236] Except that 19.4 g of 4,7-bis(4-((1,6-dimethoxynaphthyl-2-yl)oxy)butyl)-1,3-diiminobenzisisoindoline and 16.5 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline were used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminobenzisisoindoline in Synthesis Example 1, 28.1 g of green powder was obtained in the same manner as in Synthesis Example 1. The obtained compound was confirmed to be the target compound represented by the following formula (a-6) based on the consistency of the m / z values ​​of each component using liquid chromatography-mass spectrometry (LC-MS).

[0237] The toluene solution of the compound obtained in this manner exhibits maximum absorption at 735.5 nm, with a gamma of 6.30 × 10⁻⁶. 4 mL / g·cm.

[0238] [Chemistry 11]

[0239]

[0240] Furthermore, the phthalocyanine compounds (a-1) to (a-6) are all phthalocyanine compounds represented by formula (1).

[0241] <Synthetic Example 7> Synthesis of Phthalocyanine Compound (a'-1)

[0242] According to Example (65) of Japanese Patent Application Publication No. 02-138382, a comparative example phthalocyanine compound (a'-1) (maximum absorption wavelength 725 nm) represented by the following formula was synthesized.

[0243] [Chemistry 12]

[0244]

[0245] <Synthetic Example 8> Synthesis of Phthalocyanine Compound (a'-2)

[0246] Using the method described in paragraph

[0075] (Example 4) of Japanese Patent Application Publication No. 2016-204536, the comparative example phthalocyanine compound (a'-2) (maximum absorption wavelength 728 nm) represented by the following formula was synthesized.

[0247] [Chemistry 13]

[0248]

[0249] <Synthetic Example 9> Synthesis of Phthalocyanine Compound (a'-3)

[0250] Using the method described in paragraphs

[0020] to

[0025] (Example 1) of Japanese Patent Application Publication No. 05-25177, other phthalocyanine compounds for pigments represented by the following formula (a'-3) (maximum absorption wavelength 692 nm) were synthesized.

[0251] [Chemistry 14]

[0252]

[0253] <Synthetic Example 10> Synthesis of Tungsten Oxide Cesium Powder

[0254] Using the method described in paragraph

[0113] of Japanese Patent No. 4096205, cesium tungsten oxide (Cs) was synthesized.0.33 WO3) powder.

[0255] <Synthesis Example 11> Synthesis of Adhesive Resin (b-1)

[0256] In a reaction vessel, 14 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate, and 20 parts by mass of methacrylate were dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate. Then, 3 parts by mass of 2,2'-azoisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were added. After purging the reaction vessel with nitrogen, the mixture was stirred and bubbled with nitrogen while being heated at 80°C for 5 hours to obtain a solution containing adhesive resin (b-1) (adhesive resin solution (B-1): solid content concentration 35% by mass). The obtained adhesive resin (b-1) was analyzed using a gel permeation chromatography (GPC) apparatus (GPC-104 type, column: a combination of three Showa Denko LF-604 and KF-602 columns, development solvent: tetrahydrofuran) to determine the molecular weight of polystyrene. The results showed a weight-average molecular weight (Mw) of 9700, a number-average molecular weight (Mn) of 5700, and a Mw / Mn ratio of 1.70. Furthermore, in this synthetic example, the input ratio (mass ratio) of each monomer and the content ratio (mass ratio) of the structural units derived from each monomer in the obtained adhesive resin can be considered substantially the same (as in Synthetic Example 14 below).

[0257] <Synthesis Example 12> Synthesis of Adhesive Resin (b-2)

[0258] In a flask equipped with a cooling tube and a stirrer, 200 parts by mass of propylene glycol monomethyl ether were added and the temperature was raised to 80°C. At the same temperature, a mixed solution of 100 parts by mass of propylene glycol monomethyl ether, 100 parts by mass of methacrylic acid, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours. After the addition, the temperature was maintained and polymerization was carried out for 3 hours. Subsequently, the temperature of the reaction solution was raised to 100°C–120°C and the reaction was carried out for 2 hours. After cooling, 25 parts by mass of propylene glycol monomethyl ether, 116 parts by mass of 3,4-epoxycyclohexyl acrylate, and a catalyst amount of dimethylbenzylamine were added, and the temperature was raised to 110°C and the reaction was carried out for 9 hours, thereby obtaining a solution containing the binder resin (b-2) represented by the following formula (binder resin solution (B-2): solids concentration 40% by mass). The molecular weight of the resulting adhesive resin was determined in the same manner as in Synthesis Example 11. The weight average molecular weight (Mw) was 15,100, the number average molecular weight (Mn) was 7,000, and the Mw / Mn ratio was 2.16.

[0259] [Chemistry 15]

[0260]

[0261] (In the formula, the composition ratio is the mass ratio)

[0262] <Synthesis Example 13> Synthesis of Adhesive Resin (b-3)

[0263] In a flask equipped with a cooling tube and a stirrer, 200 parts by mass of propylene glycol monomethyl ether were added and the temperature was raised to 80°C. At the same temperature, a mixed solution of 200 parts by mass of propylene glycol monomethyl ether, 67 parts by mass of methacrylic acid, 33 parts by mass of N-cyclohexylmaleimide, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours. After the addition, the temperature was maintained and polymerization was carried out for 3 hours. Subsequently, the temperature of the reaction solution was raised to 100°C–120°C and the reaction was carried out for another 3 hours. After cooling, 28 parts by mass of propylene glycol monomethyl ether, 119 parts by mass of 3,4-epoxycyclohexyl methyl acrylate, and a catalyst amount of dimethylbenzylamine were added, and the temperature was raised to 110°C and the reaction was carried out for 30 hours, thereby obtaining a solution containing the binder resin (b-3) represented by the following formula (binder resin solution (B-3): solids concentration 40% by mass). The molecular weight of the resulting adhesive resin was determined in the same manner as in Synthesis Example 11. The weight-average molecular weight (Mw) was 17,000, the number-average molecular weight (Mn) was 7,700, and the Mw / Mn ratio was 2.21.

[0264] [Chemistry 16]

[0265]

[0266] (In the formula, the composition ratio is the mass ratio)

[0267] <Synthesis Example 14> Synthesis of Adhesive Resin (b-4)

[0268] In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2-azobisisobutyronitrile, 140 parts by mass of methyl 3-methoxypropionate, and 60 parts by mass of propylene glycol monomethyl ether were added. Then, 32 parts by mass of glycidyl methacrylate, 40 parts by mass of 3-methacryloyloxypropyltriethoxysilane, 11 parts by mass of benzyl methacrylate, 3 parts by mass of n-butyl methacrylate, and 14 parts by mass of methacrylic acid were added. After nitrogen purging, the mixture was slowly stirred, and the temperature of the solution was raised to 80°C. Polymerization was carried out at this temperature for 5 hours, thereby obtaining a solution containing binder resin (b-4) (hereinafter, binder resin solution (B-4) has a solid content concentration of 35% by mass). The molecular weight of the obtained binder resin was determined in the same manner as in Synthesis Example 11, and the results showed a weight average molecular weight (Mw) of 9500, a number average molecular weight (Mn) of 5800, and a Mw / Mn ratio of 1.64.

[0269] <Synthetic Example 15> Dispersant (d-2)

[0270] Using the method described in the literature (Macromolecules 1992, 25, pp. 5907-5913), 45 parts by weight of dimethylaminoethyl methacrylate, 20 parts by weight of 2-ethylhexyl methacrylate, 5 parts by weight of n-butyl methacrylate, and PME-200 (methoxy polyethylene glycol monomethacrylate and CH2=C(CH3)COO(C2H4O)) were mixed. n 30 parts by mass of a polymer of monomers represented by -CH3(n≒4) were co-polymerized to obtain a reaction solution containing an inert copolymer. The reaction solution was then quenched with methanol, and the resulting reaction solution was washed with a 7% by mass sodium bicarbonate aqueous solution, followed by water. Subsequently, by solvent substitution with propylene glycol monomethyl ether acetate (PGMEA), a dispersant solution (D-2) containing dispersant (d-2) was obtained in 80% by mass. The resulting dispersant (d-2) had an amine value of 160 mg KOH / g, a Mw of 9500, a Mw / Mn ratio of 1.21, and a solids content of 39.6% by mass in the dispersant solution (D-2).

[0271] [Preparation Example 1] Preparation of Dispersion (C-1)

[0272] Prepare 25.00 parts by mass of cesium tungsten oxide, 13.30 parts by mass of BYK-LPN6919 (60% by mass solid content, 120 mg KOH / g amine value) from BYK-Chemie as dispersant (d-1), and 61.70 parts by mass of cyclopentanone (CPN) as solvent (dispersion medium). These were then packed together with 2000 parts by mass of 0.1 mm diameter zirconium oxide particles into a container and dispersed using a paint shaker to obtain a dispersion (C-1) with an average particle size (D50) of 19 nm. Furthermore, the average particle size was determined using a light scattering apparatus (ALV-5000 from ALV GmbH, Germany) and the dynamic light scattering (DLS) method.

[0273] [Preparation Example 2] Preparation of Dispersion (C-2)

[0274] Except for changing the dispersant solution (D-2) to 20.20 parts by mass and the solvent to 54.80 parts by mass of CPN, a dispersion (C-2) with an average particle size of 19 nm was obtained in the same manner as in Preparation Example 1.

[0275] [Preparation Example 3] Preparation of pigment solutions (A-1) to (A-9)

[0276] 5.00 parts by mass of phthalocyanine compound (a-1) and 95.00 parts by mass of CPN as solvent were measured into a container and mixed using a stirrer. The resulting solution was pressure filtered using a 0.2 μm polytetrafluoroethylene (PTFE) filter under a pressure of 0.05 MPa to obtain pigment solution (A-1). In addition, pigment solutions (A-2) to (A-6), (A-8), and (A-9) as described in Table 1 were obtained using the same method, except that phthalocyanine compounds (a-2) to (a-6), (a-8), and (a-9) were used respectively.

[0277] The pigment solution (A-7) was prepared in the same manner, except that 4.50 parts by mass of phthalocyanine compound (a-1), 1.20 parts by mass of phthalocyanine compound (a'-3), and 94.30 parts by mass of CPN as solvent were used.

[0278] [Example 1]

[0279] In a container, measure out 20.00 parts by weight of the dispersion (C-1), 23.15 parts by weight of the pigment solution (A-1), 21.01 parts by weight of the binder resin solution (B-1), 8.14 parts by weight of KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) from Nippon Kayaku Co., Ltd. as the polymerization compound, 1.53 parts by weight of NCI-930 (an O-acyl oxime compound) from ADEKA Co., Ltd. as the polymerization initiator, 0.05 parts by weight of FTX-218D (a fluorinated surfactant) from NEOS Co., Ltd. as the surfactant, and Karenz MT from Showa Denko Co., Ltd. as the reaction modifier. 0.31 parts by weight of PE1 (polyfunctional thiol), 0.10 parts by weight of BASF's Irganox 1010 (phenolic antioxidant) as an antioxidant, and 25.71 parts by weight of cyclopentanone (CPN) as a solvent were mixed using a stirrer. Approximately 100 mL of the mixture was then pressure filtered through a 0.5 μm polytetrafluoroethylene (PTFE) filter under a pressure of 0.05 MPa to obtain the composition of Example 1.

[0280] [Examples 2-13, Comparative Examples 1-3]

[0281] Except that the total amount and mixing amount (parts by mass) of the dispersion, pigment solution, and binder resin solution, as well as the mixing amount (parts by mass) of the polymerizable compound, polymerization initiator, surfactant, reaction modifier, antioxidant, and solvent are shown in Table 1, the compositions of Examples 2 to 13 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1. Furthermore, Table 1 also shows the types and contents of [A] phthalocyanine compound, [B] binder resin, [C] infrared shielding agent, [D] dispersant, and other pigments in the obtained compositions. "CsWO" in Table 1 indicates cesium tungsten oxide (CsWO) obtained in Synthesis Example 10. 0.33 WO3).

[0282] [evaluate]

[0283] The obtained compositions were evaluated as follows. The evaluation results are shown in Table 1.

[0284] Each composition was spin-coated onto a glass substrate to a specified film thickness. Subsequently, the coating was heated at 100°C for 120 seconds and then subjected to a stepper motor with an I-ray pressure of 500 mJ / cm². 2Exposure was performed using the following method. Then, an infrared shielding film with an average thickness of 2.0 μm to 4.0 μm was fabricated on a glass substrate by heating at 220°C for 300 seconds. The average film thicknesses are shown in Table 1. Furthermore, the film thickness was measured using a stylus-type step meter (Yamato Scientific's "α-Step IQ"). Next, the transmittance of the infrared shielding film fabricated on the glass substrate was measured in each wavelength region using a spectrophotometer (Nippon Spectrophotometer's "V-7300") in comparison with the glass substrate. Based on the obtained spectra, the film was evaluated according to the evaluation criteria described below.

[0285] (Visible light transmittance)

[0286] The average transmittance from 430nm to 580nm was calculated. When the average transmittance is less than 70%, the sensitivity decreases when used as an infrared shielding film. Furthermore, the average transmittance was evaluated using the following criteria.

[0287] A: More than 80%

[0288] B: 70% or more but less than 80%

[0289] C: Less than 70%

[0290] (Visible through the window area)

[0291] The transmittance in the 430nm-580nm range was determined to be continuously above 70%. When the range of continuously above 70% is 175nm or higher, it is predicted to have high practicality when used as an infrared shielding film due to its high sensitivity. Furthermore, the visible transmission window range was evaluated using the following criteria.

[0292] A: Above 200nm

[0293] B: 175nm or higher but less than 200nm

[0294] C: Less than 175nm

[0295] (Infrared shielding range)

[0296] The transmittance in the 700nm-800nm ​​range was determined to be continuously below 20%. When the range of continuously below 20% is greater than 20nm, it is predicted to be highly practical when used as an infrared shielding film due to its high noise shielding capability. Furthermore, the infrared shielding range was evaluated using the following criteria.

[0297] A: 30nm and above

[0298] B: 20nm or higher but less than 30nm

[0299] C: Less than 20nm

[0300] (Average skewness (Off-Slope))

[0301] Within the 500nm-750nm range, the longest wavelength with transmittance of 80% or more is defined as (X), and the shortest wavelength with transmittance of 20% or less is defined as (Y). The average Off-Slope (Z) is calculated using the following formula. When the average Off-Slope is 0.45 or higher, it is speculated that when used as an infrared shielding film, it can improve the color reproduction and noise masking function of the obtained image, making it highly practical. Furthermore, the average Off-Slope is evaluated using the following criteria.

[0302] (Z)=60 / ((Y)-(X))

[0303] AA: 0.60 or above

[0304] A: 0.50 or higher but less than 0.60

[0305] B: 0.45 or higher but less than 0.50

[0306] C: Less than 0.45

[0307] (Heat resistance)

[0308] Regarding the infrared shielding film fabricated on the glass substrate, it was heated at 260°C for 300 seconds using a hot plate, and the transmittance in each wavelength region before and after heating was measured using a spectrophotometer (Japan Spectrophotometer Co., Ltd.'s "V-7300") on the glass substrate. The absorbance of the infrared shielding film at the wavelength with the lowest transmittance in the 700nm-800nm ​​range was defined as (A1), and the absorbance at the same wavelength after heating to 260°C was defined as (A2). The absorbance retention rate was calculated as 100 × (A1) / (A2), and the heat resistance at 260°C was evaluated using the following criteria. If the retention rate is 30% or higher, it is speculated that when used as an infrared shielding film, it can maintain high heat resistance and has high practicality when used in conjunction with protective films, etc. Furthermore, the retention rate was evaluated using the following criteria.

[0309] AA: above 90%

[0310] A: 60% or more but less than 90%

[0311] B: 30% or more but less than 60%

[0312] C: Less than 30%

[0313] (Defect suppression)

[0314] The compositions were spin-coated onto a silicon substrate, and the coating was hardened to form a hardened film with a thickness of approximately 1 μm. The defect density of the hardened film was measured using a defect / foreign object inspection device (KLA-Tencor "KLA 2351"). It was determined that the lower the defect density value, the higher the defect suppression performance. Furthermore, a defect is defined as a detection point with a size of 1 μm or larger. Based on the defect density, the defect suppression performance was evaluated using the following criteria.

[0315] A: 10 / cm 2 the following

[0316] B: Exceeding 10 / cm 2 And it is 50 / cm 2 the following

[0317] C: Over 50 / cm 2

[0318] (Post Coating Delay (PCD) stability)

[0319] Each composition was spin-coated onto a silicon substrate to form a coating film approximately 1 μm thick without hardening. The defect density of the coating film was measured using a defect / foreign matter inspection device (KLA-Tencor "KLA 2351"). Subsequently, the defect density of the coating film was measured at regular intervals, and the time it took for the number of defects to increase by more than 20% relative to the initial value was used to evaluate the post-coating delay (PCD) stability of the coating film. Regarding PCD stability, a higher estimated value indicates greater practicality.

[0320] A: More than 24 hours

[0321] B: More than 12 hours but less than 24 hours

[0322] C: Less than 12 hours

[0323]

[0324] As shown in Table 1, the visible light transmittance, visible light transmission window range, infrared shielding range, average off-slope, heat resistance, defect suppression, and PCD stability of Examples 1 to 13 were all evaluated as good. Furthermore, it is known that in the examples using the phthalocyanine compounds represented by formula (1), Examples 1, 3 to 6, which used phthalocyanine compounds with substituents R (a-1, a-3 to a-6), exhibited higher heat resistance compared to Example 2, which used phthalocyanine compounds without substituents R (a-2). Additionally, it is also known that in the examples using phthalocyanine compounds with substituents R, Examples 1, 3, and 4 also showed good visible light transmittance.

[0325] Industrial availability

[0326] The optical sensor composition of the present invention can preferably be used as a forming material for optical filters of optical sensors such as solid-state imaging elements.

Claims

1. A composition for an optical sensor, comprising: The phthalocyanine compound represented by formula (1) below; and Adhesive resin, In formula (1), each R is independently an alkyl group with or without a substituent, or an aryl group with or without a substituent; each X is independently a hydrogen atom, a halogen atom, or an alkyl group; each X may also be bonded to each other and together with these bonded carbon chains to form an aromatic ring; M is two hydrogen atoms, a divalent metal atom, a derivative of a trivalent metal atom, or a derivative of a tetravalent metal atom, wherein the divalent metal atom is selected from Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, Pb, and the derivative of the trivalent metal atom or the derivative of the tetravalent metal atom is selected from AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl2, SiBr2, SiI2, Si(OH)2, GeCl2, GeBr2, GeI2, SnCl2, SnBr2, SnI2, Sn(OH)2, TiO; each n is independently an integer from 3 to 6.

2. The composition for optical sensors according to claim 1, wherein the plurality of Rs are each independently an alkyl group having a substituent or an aryl group having a substituent.

3. The composition for optical sensors according to claim 1 or 2, wherein the adhesive resin has oxetyl, oxetyl, (meth)acryloyl, alkoxysilyl, or combinations thereof.

4. The composition for optical sensors according to claim 1 or 2, wherein the adhesive resin has a ring structure in the main chain.

5. The composition for optical sensors according to claim 1 or 2, wherein the alkyl and aryl groups represented by the plurality of Rs have substituents having heteroatoms.

6. The composition for optical sensors according to claim 5, wherein the substituent is a halogen atom, methoxy, ethoxy, methylthio, ethylthio, or a combination thereof.

7. The composition for an optical sensor according to claim 1 or 2, further comprising an infrared shielding agent. The infrared shielding agent is a metal oxide, a copper compound, or a combination thereof, except that the copper compound is the phthalocyanine compound.

8. The composition for an optical sensor according to claim 7, wherein the metal oxide is cesium tungsten oxide.

9. A composition for an optical sensor comprising a phthalocyanine compound represented by the following formula (2): In formula (2), each R is independently an alkyl group with a substituent or an aryl group with a substituent; each X is independently a hydrogen atom, a halogen atom or an alkyl group; each X may also be bonded to each other and form an aromatic ring together with the bonded carbon chain; M is two hydrogen atoms, a divalent metal atom, a derivative of a trivalent metal atom or a derivative of a tetravalent metal atom, wherein the divalent metal atom is selected from Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, Pb, and the derivative of the trivalent metal atom or the derivative of the tetravalent metal atom is selected from AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl2, SiBr2, SiI2, Si(OH)2, GeCl2, GeBr2, GeI2, SnCl2, SnBr2, SnI2, Sn(OH)2, TiO; each n is independently an integer from 3 to 6.

10. The composition for an optical sensor according to claim 9, wherein the alkyl and aryl groups represented by the plurality of Rs have substituents that are heteroatoms.

11. The composition for an optical sensor according to claim 10, wherein the substituent is a halogen atom, methoxy, ethoxy, methylthio, ethylthio, or a combination thereof.

12. The composition for an optical sensor according to any one of claims 9 to 11, further comprising an infrared shielding agent. The infrared shielding agent is a metal oxide, a copper compound, or a combination thereof, except that the copper compound is the phthalocyanine compound.

13. The composition for an optical sensor according to claim 12, wherein the metal oxide is cesium tungsten oxide.

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