Optical sensor composition

Abstract

To provide a composition for an optical sensor which can form an optical filter for an optical sensor which is free from such defects as foreign substances and having an excellent characteristic regarding the transmittance of visible light and the shielding property of infrared rays.SOLUTION: The composition of an optical sensor includes a phthalocyanine compound expressed by a specific chemical formula and a binder resin having a (meth)acryloyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for an optical sensor. [Background technology]

[0002] Video cameras, digital cameras, mobile phones with camera functions, and the like are equipped with solid-state imaging elements, which are optical sensors. Specific examples of solid-state imaging elements include CCD (Charge-Coupled Device) image sensors and CMOS (Complementary MOS) image sensors. The sensitivity of the photodiodes included in these solid-state imaging elements ranges from the visible light region to the infrared region. For this reason, solid-state imaging elements are provided with filters to block infrared rays. This optical filter (infrared blocking filter) can correct the sensitivity of the solid-state imaging element to be closer to the visual sensitivity of humans. Similarly, filters to block infrared rays may be provided in optical sensors other than solid-state imaging elements.

[0003] The optical filter contains a dye or pigment as an infrared shielding agent. The infrared shielding agent is required to have the property of absorbing infrared rays while sufficiently transmitting visible light. As one of such infrared shielding agents, the use of a phthalocyanine compound has been studied as a good shielding agent for near infrared rays in particular (see JP 2008-201952 A). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-201952 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in conventional optical filters using phthalocyanine compounds, defects such as foreign matter may occur due to the influence of compatibility, etc. Such defects may affect the visible light transmittance, infrared shielding properties, etc. of the optical filter. In addition, when forming an infrared shielding film for an optical filter by coating a composition containing a dye such as a phthalocyanine compound, if the coating is left for a long time, defects such as foreign matter are likely to occur in the obtained infrared shielding film. In terms of the production process, it is desired to obtain an infrared shielding film with few defects such as foreign matter even if the film is left for a while after coating and then cured.

[0006] Furthermore, conventional optical filters are not fully satisfied in terms of visible light transmittance and infrared shielding. Specifically, when an optical filter is used as an infrared blocking filter for an optical sensor such as a solid-state imaging device, it is required that the optical filter not only has a high visible light transmittance and a low infrared transmittance, but also has a wide wavelength region with high visible light transmittance and a wide wavelength region with low infrared transmittance, and that the wavelength region with high visible light transmittance and the wavelength region with low infrared transmittance are close to each other. When an optical filter having such characteristics is used in an optical sensor such as a solid-state imaging device, it is possible to improve sensitivity, noise shielding function, color reproducibility, etc.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for optical sensors capable of forming an optical filter for an optical sensor having few defects such as foreign matter and good properties with respect to visible light transmittance and infrared shielding properties. [Means for solving the problem]

[0008] The invention made to solve the above problems is a composition for optical sensors, which contains a phthalocyanine compound represented by the following formula (1) and a binder resin. [ka] (In formula (1), each of the R's is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Each of the X's is independently a hydrogen atom, a halogen atom, or an alkyl group. The X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the n's is independently an integer of 3 to 6.)

[0009] Another invention made to solve the above problems is a composition for optical sensors containing a phthalocyanine compound represented by the following formula (2). [ka] (In formula (2), each of the R's is independently an alkyl group having a substituent, or an aryl group having a substituent. Each of the X's is independently a hydrogen atom, a halogen atom, or an alkyl group. The X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the n's is independently an integer of 3 to 6.) Effect of the Invention

[0010] According to the present invention, it is possible to provide a composition for optical sensors which can form an optical filter for an optical sensor having few defects such as foreign matter and excellent properties in terms of visible light transmittance and infrared shielding properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, a composition for an optical sensor according to one embodiment of the present invention will be described in detail.

[0012] <Composition for optical sensors (I)> A composition for optical sensors (I) according to one embodiment of the present invention (hereinafter, also simply referred to as "composition (I)") contains a phthalocyanine compound [A1] and a binder resin [B]. It is preferable that the composition further contains an infrared shielding agent [C] which is a metal oxide, a copper compound (excluding the phthalocyanine compound [A]) or a combination thereof.

[0013] ([A1] Phthalocyanine compound) The phthalocyanine compound [A1] is a compound represented by the following formula (1). The phthalocyanine compound [A1] has high transmittance in the visible light region (for example, a wavelength region of 430 nm or more and 580 nm or less), while having high shielding properties in the near-infrared region (for example, a wavelength region of 700 nm or more and 800 nm or less). In addition, the phthalocyanine compound [A1] has excellent compatibility with other components. Since the composition (I) contains the phthalocyanine compound [A1], it is possible to form an optical filter having few defects such as foreign matter and having good properties regarding visible light transmittance and infrared shielding properties.

[0014] [ka]

[0015] In formula (1), each of the R's is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Each of the X's is independently a hydrogen atom, a halogen atom, or an alkyl group. Each of the X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the n's is independently an integer of 3 to 6.

[0016] Examples of the alkyl group represented by R include linear or branched alkyl groups having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. The upper limit of the carbon number of this alkyl group is preferably 12, more preferably 8, and further preferably 4.

[0017] The aryl group represented by R includes a monovalent group consisting of only an aromatic ring, and a monovalent group consisting of an aromatic ring and an alkyl group bonded thereto. Specific 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 aryl group is preferably a group consisting of only an aromatic ring, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group from the viewpoint of visible light transmittance and the like.

[0018] From the standpoint of the heat resistance of the resulting optical filter, the above R is preferably a substituted or unsubstituted aryl group.

[0019] The alkyl group and aryl group represented by each of the above-mentioned multiple R may or may not have a substituent, but it is preferable that they have a substituent. That is, it is preferable that each of the above-mentioned multiple R is independently an alkyl group having a substituent or an aryl group having a substituent. In this way, when the above-mentioned multiple R have a substituent, the compatibility of the phthalocyanine compound [A1] is further improved, defects such as foreign matter in the obtained optical filter are further suppressed, and the properties related to visible light transmittance and infrared shielding properties are also improved. Furthermore, when the above-mentioned multiple R have a substituent, the heat resistance of the obtained optical filter is also improved.

[0020] The substituents that the alkyl group and aryl group represented by each of the above multiple Rs may have may be hydrocarbon groups such as alkenyl groups and alkynyl groups, but are preferably groups having heteroatoms. Heteroatoms refer to atoms other than hydrogen and carbon atoms. When the alkyl group and aryl group represented by each of the above multiple Rs have a substituent having a heteroatom, the compatibility and the like are further improved, defects such as foreign matter in the obtained optical filter are further suppressed, and the properties related to visible light transmittance and infrared shielding properties are also improved. Furthermore, when the above multiple Rs have a substituent having a heteroatom, the heat resistance of the obtained optical filter is also improved. As the heteroatom, a halogen atom, an oxygen atom, and a sulfur atom are preferable, and a halogen atom and an oxygen atom are more preferable.

[0021] Examples of the substituent having a hetero atom include a halogen atom, an alkoxy group, an alkylthio group, a cyano group, a nitro group, a carboxy group, a hydroxy group, a thiol group, and an amino group.

[0022] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, with a fluorine atom being preferred.

[0023] Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Of these, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

[0024] Examples of the alkylthio group include a methylthio group (CH3-S-), an ethylthio group (C2H5-S-), and a propylthio group (C3H7-S-), with the methylthio group and the ethylthio group being more preferred.

[0025] Among the substituents having a hetero atom, a halogen atom, an alkoxy group, and an alkylthio group are preferred, and a halogen atom and an alkoxy group are more preferred. Also preferred are a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, or a combination thereof.

[0026] The above multiple R's may be the same or different, but are preferably the same.

[0027] Examples of the halogen atom represented by X include those exemplified above as the halogen atom for the substituent.

[0028] Examples of the alkyl group represented by X include those exemplified as the alkyl group represented by R.

[0029] The above-mentioned multiple Xs may be bonded to each other. Usually, among the multiple Xs, 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 formed include a benzene ring, a naphthalene ring, and an anthracene ring. The hydrogen atoms of these aromatic rings may be substituted with a hydrocarbon group or other substituents.

[0030] The above X is preferably a hydrogen atom. In addition, multiple X may be the same or different, but are preferably the same.

[0031] 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 refers to a metal atom that can become a divalent cation.

[0032] Here, the derivative of a metal atom refers to an atomic group containing a metal atom. A trivalent metal atom refers to a metal atom that can become a trivalent cation. Examples of trivalent metal atoms include Al and In. A tetravalent metal atom refers to a metal atom that can become a tetravalent cation. Examples of tetravalent metal atoms include Si, Ge, and Sn. Metal atoms also include semimetal atoms. Examples of derivatives of 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.

[0033] As the above-mentioned M, H2 (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl2, AlCl, VO and TiO are preferable, and VO is more preferable.

[0034] The lower limit of the above n is preferably 4. The upper limit of the above n is preferably 5, and more preferably 4. Multiple n's may be the same or different, but are preferably the same.

[0035] The lower limit of the maximum absorption wavelength of the phthalocyanine compound [A1] is preferably 680 nm, more preferably 700 nm, and even more preferably 720 nm. Meanwhile, the upper limit of this maximum absorption wavelength is preferably 1,000 nm, more preferably 900 nm, more preferably 800 nm, and even more preferably 750 nm. By having the maximum absorption wavelength of the phthalocyanine compound [A1] within the above range, an optical filter having better properties regarding visible light transmittance and infrared shielding properties can be formed.

[0036] The synthesis method of the phthalocyanine compound [A1] is not particularly limited, and the compound can be synthesized by combining known methods. For example, the compound can be synthesized by reacting a phthalonitrile compound represented by the following formula (i) or a 1,3-diiminoisoindoline compound represented by the following formula (ii) with a metal or a metal derivative.

[0037] [ka]

[0038] In formulae (i) and (ii), R, X and n are defined as in formula (1).

[0039] 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 preferably used. Examples of these include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, iron 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, and tin chloride.

[0040] The reaction temperature is, for example, 60 to 300°C, and preferably 100 to 220°C. The reaction time is, for example, 30 minutes to 72 hours, and preferably 1 hour to 48 hours. In the reaction, it is preferable to use a solvent. As the solvent used in the reaction, an organic solvent having a boiling point of 60°C or higher is preferable, and an organic solvent having a boiling point of 80°C or higher is more preferable.

[0041] Examples of the organic solvent to be used include alcohol solvents such as methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, n-hexanol, 1-heptanol, 1-octanol, 1-dodecanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylethanol, and diethylethanol; and high-boiling point solvents such as dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, DMI (1,3-dimethyl-2-imidazolidinone), and urea.

[0042] The reaction is carried out in the presence or absence of a catalyst, preferably in the presence of a catalyst, such as inorganic catalysts such as ammonium molybdate, or basic organic catalysts such as DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) and DBN (1,5-diazabicyclo[4.3.0]non-5-ene).

[0043] In the case of a phthalocyanine compound in which M in formula (1) is two hydrogen atoms, the compound can be produced 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 above-mentioned reaction conditions, and then subjecting the central metal, sodium or potassium, to desorption treatment with hydrochloric acid, sulfuric acid, or the like.

[0044] After the reaction is completed, the solvent is distilled off or the reaction solution is poured into a poor solvent for the phthalocyanine compound to precipitate the target product, and the precipitate is filtered to obtain the phthalocyanine compound represented by formula (1). If necessary, the target product can be further purified by a known purification method such as recrystallization or column chromatography to obtain a target product of higher purity.

[0045] The phthalonitrile compound represented by formula (i) and the 1,3-diiminoisoindoline compound represented by formula (ii) can be synthesized by referring to a known method, for example, by referring to the method described in JP-A-2003-516421.

[0046] The lower limit of the content of the phthalocyanine compound [A1] in the total solid content (all components other than the solvent) in the composition (I) is preferably 0.1% by mass, more preferably 0.5% by mass, even more preferably 1% by mass, and even more preferably 2% by mass. On the other hand, the upper limit of this 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 phthalocyanine compound [A1] within the above range, the properties of the obtained optical filter regarding visible light transmittance and infrared shielding property become better.

[0047] The phthalocyanine compound (A1) may be used alone or in combination of two or more kinds.

[0048] ([B] Binder resin) The binder resin [B] is a component that holds the phthalocyanine compound [A1] and the like in the resulting optical filter and serves as a matrix.

[0049] The binder resin [B] preferably has a polymerizable group, and more preferably has a structural unit containing a polymerizable group, in order to improve strength, sensitivity, heat resistance, etc. Examples of the polymerizable group include an oxiranyl group, an oxetanyl group, a (meth)acryloyl group, a vinyl group, and an alkoxysilyl group, and is preferably an oxiranyl group, an oxetanyl group, a (meth)acryloyl group, an alkoxysilyl group, or a combination thereof, and more preferably a (meth)acryloyl group.

[0050] Examples of monomers that provide structural units containing a polymerizable group include glycidyl (meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl (meth)acrylate, 3-methacryloxypropyltriethoxysilane, and the like.

[0051] In addition, for example, a structural unit containing a polymerizable group can also be introduced by reacting a resin having a structural unit containing a carboxy group with a compound having a group that reacts with the carboxy group (such as an oxiranyl group or an oxetanyl group) and a polymerizable group such as a (meth)acryloyl group.

[0052] The lower limit of the content of the structural unit having a polymerizable group in the binder resin [B] is preferably 5% by mass, more preferably 10% by mass, further preferably 15% by mass, and even more preferably 30% by mass, 50% by mass, or 75% by mass, relative to 100% by mass of the binder resin [B]. On the other hand, the upper limit of this content is preferably 95% by mass, more preferably 90% by mass, and further preferably 85% by mass.

[0053] The binder resin [B] preferably has a ring structure in the main chain to improve heat resistance. The number of ring members in this ring structure may be, for example, 3 to 12, and preferably 5 to 8.

[0054] Examples of monomers that provide structural units containing a ring structure in the main chain include N-substituted maleimide monomers and cycloolefins.

[0055] The N-substituted maleimide monomer is a compound in which the hydrogen atom bonded to the nitrogen atom in maleimide is replaced by a substituent. The substituent is preferably a hydrocarbon group, more preferably a hydrocarbon group having a ring structure, and more preferably an aromatic hydrocarbon group. Examples of the N-substituted maleimide monomer include N-phenylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, and N-methylmaleimide.

[0056] Examples of the cycloolefin include norbornene-based olefins, tetracyclododecene-based olefins, and dicyclopentadiene-based olefins.

[0057] In addition, a phenol resin or the like can also be used as the binder resin having a ring structure in the main chain.

[0058] The content of the structural unit having a ring structure in the main chain in the binder resin [B] is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, relative to 100% by mass of the binder resin [B].

[0059] [B] The binder resin preferably contains an acidic group. Examples of the acidic group include a carboxy group, an acid anhydride group, a phenolic hydroxyl group, and a sulfo group. Among the above, the acidic group is preferably a carboxy group. [B] The binder resin is preferably a resin containing a structural unit having one or more acidic groups. When the binder resin [B] has an acidic group, it can exhibit good alkali solubility. When the binder resin [B] has alkali solubility, it can be developed in an alkali and an optical filter having a desired pattern shape can be formed.

[0060] Examples of monomers that provide structural units containing an acidic group include monomers having a carboxy group, such as unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl]esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; and mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate.

[0061] Examples of the monomer having a phenolic hydroxyl group include 4-vinylphenol, 4-isopropenylphenol, and 4-hydroxyphenyl(meth)acrylate.

[0062] The content of the structural unit containing an acidic group in the binder resin [B] is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass, relative to 100% by mass of the binder resin [B].

[0063] The binder resin [B] may further contain other structural units. Examples of monomers that provide other structural units include Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (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 (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] (meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane; Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ] Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; Examples of the polymer include macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

[0064] The binder resin [B] can be obtained by polymerizing the above-mentioned monomers by a known method. The binder resin [B] may be used alone or in combination of two or more kinds.

[0065] The weight average molecular weight (Mw) of the binder resin [B] in terms of polystyrene, as measured 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. When the Mw is within the above range, the binder resin [B] can have excellent solubility in solvents and developers and sufficient mechanical properties.

[0066] The lower limit of the content of the binder resin [B] in the total solid content of the composition (I) is preferably 5 mass%, more preferably 10 mass%, and even more preferably 20 mass%. On the other hand, the upper limit of this content is preferably 70 mass%, more preferably 60 mass%, and even more preferably 50 mass%. By setting the content of the binder resin [B] within the above range, the obtained optical filter can fully exhibit the properties related to visible light transmittance and infrared shielding property, while also improving heat resistance, etc.

[0067] ([C] Infrared shielding agent) The infrared shielding agent [C] is a metal oxide, a copper compound (excluding the phthalocyanine compound [A1]), or a combination thereof. The infrared shielding agent [C] is preferably a compound having a maximum absorption wavelength in the range of 800 nm to 2000 nm. By using such an infrared shielding agent [C] in combination with the phthalocyanine compound [A1], the infrared shielding performance of the obtained optical filter is further improved.

[0068] [C] Examples of metal oxides as infrared shielding agents include tungsten oxide compounds, quartz (SiO2), magnetite (Fe3O4), alumina (Al2O3), titania (TiO2), zirconia (ZrO2), and spinel (MgAl2O4).

[0069] [C] Examples of the copper compound as an infrared shielding agent include copper phthalocyanine compounds and other copper complexes. Examples of the copper phthalocyanine compounds include copper phthalocyanine, chlorinated copper phthalocyanine, chlorinated brominated copper phthalocyanine, and brominated copper phthalocyanine.

[0070] [C] The infrared shielding agent is preferably a metal oxide, more preferably a tungsten oxide compound. Tungsten oxide compounds are infrared shielding agents that have high absorption (i.e., high infrared shielding properties) for infrared rays (particularly infrared rays having a wavelength of about 800 nm or more and 1200 nm or less) and low absorption for visible light. Therefore, by containing a tungsten oxide compound in the composition (I), the obtained optical filter can have high infrared shielding properties while maintaining good visible light transmittance. [C] The infrared shielding agent may be used alone or in combination of two or more kinds.

[0071] The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following formula (3). A x WO y (3)

[0072] In formula (3), A is a metal element. 0.001≦x≦1.1. 2.2≦y≦3.0.

[0073] Examples of the metal element represented by A in the above 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. The metal element represented by A may be one type or two or more types.

[0074] The above A is preferably an alkali metal, more preferably Rb or Cs, and further preferably Cs. That is, the metal oxide is more preferably cesium tungsten oxide.

[0075] In the above formula (3), x is 0.001 or more, so that infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, and more preferably 0.1. On the other hand, x is 1.1 or less, so that the generation of an impurity phase in the tungsten oxide-based compound can be more reliably prevented. The upper limit of x is preferably 1, and more preferably 0.5.

[0076] When y in the above formula (3) is 2.2 or more, the chemical stability of the material can be further improved. The lower limit of y is preferably 2.5. On the other hand, when y is 3.0 or less, infrared rays can be sufficiently shielded.

[0077] Specific examples of the tungsten oxide compound represented by the above formula (3) include Cs 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 WO3, etc., and Cs 0.33 WO3 and Rb 0.33 WO3 is preferred, Cs 0.33 WO3 is more preferred.

[0078] [C] The infrared shielding agent is preferably fine particles. The upper limit of the average particle size (D50) of the infrared shielding agent [C] is preferably 500 nm, more preferably 200 nm, even more preferably 50 nm, and even more preferably 30 nm. By having the average particle size below the upper limit, the visible light transmittance can be further improved. On the other hand, for reasons such as ease of handling during production, the average particle size of the infrared shielding agent [C] is usually 1 nm or more, and may be 10 nm or more.

[0079] [C] The infrared shielding agent can be synthesized by a known method, but is also 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, for example, by a method of heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. In addition, the tungsten oxide-based compound is also available as a dispersion of tungsten fine particles, such as "YMF-02" by Sumitomo Metal Mining Co., Ltd.

[0080] The lower limit of the content of the infrared shielding agent [C] in the total solid content in the composition (I) is preferably 1 mass%, more preferably 5 mass%, even more preferably 10 mass%, and even more preferably 15 mass%. On the other hand, the upper limit of this content is preferably 70 mass%, more preferably 50 mass%, even more preferably 40 mass%, and even more preferably 30 mass%. By setting the content of the infrared shielding agent [C] within the above range, the properties of the visible light transmittance and infrared shielding property of the obtained optical filter become better.

[0081] The lower limit of the mass ratio ([C] / [A1]) of the content of the infrared shielding agent [C] to the content of the phthalocyanine compound [A1] is preferably 1, more preferably 2, and more preferably 3. On the other hand, the upper limit of this mass ratio ([C] / [A1]) is preferably 40, more preferably 20, and even more preferably 10. By setting the content ratio of the phthalocyanine compound [A1] to the infrared shielding agent [C] within the above range, the properties of the obtained optical filter relating to visible light transmittance and infrared shielding property become better.

[0082] ([D] Dispersant) The composition (I) preferably further contains a dispersant [D], which enhances uniform dispersion of the infrared shielding agent [C] (particularly, a metal oxide), thereby improving the visible light transmittance and infrared shielding properties of the resulting optical filter.

[0083] [D] The dispersant may, for example, be a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkyl phenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, or a (meth)acrylic-based dispersant. Among these, a (meth)acrylic-based dispersant is preferred. [D] The dispersant is preferably a block copolymer.

[0084] [D] The dispersant can be commercially available. For example, (meth)acrylic dispersants include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, and BYK-LPN22102 (all manufactured by BYK). Urethane dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182. , Disperbyk-2164 (all manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol Corporation), as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Corporation), as a polyester-based dispersant, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), as well as BYK-LPN21324 (manufactured by BYK), etc. can be mentioned.

[0085] The lower limit of the amine value of the dispersant [D] 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 this amine value is preferably 300 mgKOH / g, more preferably 200 mgKOH / g, and even more preferably 160 mgKOH / g. By using a dispersant having such an amine value, the dispersibility of the infrared shielding agent [C] is improved, and the properties of the obtained optical filter can be further improved. The "amine value" is the number of mg of KOH equivalent to HCl required to neutralize 1 g of the dispersant solid content.

[0086] The lower limit of the content of the dispersant [D] is preferably 5 parts by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass, relative to 100 parts by mass of the infrared shielding agent [C], while 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.

[0087] ([E] Polymerizable compound) The composition (I) preferably further contains a polymerizable compound [E]. When the composition (I) contains a polymerizable compound [E], it can exhibit good curability and good heat resistance of the optical filter obtained. The polymerizable compound [E] refers to a compound having two or more polymerizable groups. The binder resin [B] having two or more polymerizable groups is not included in the polymerizable compound [E]. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. The polymerizable compound [E] is preferably a compound having two or more (meth)acryloyl groups and a compound having two or more N-alkoxymethylamino groups, and more preferably a compound having two or more (meth)acryloyl groups. The polymerizable compound [E] can be used alone or in combination of two or more.

[0088] Examples of compounds having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates which are reaction products between an aliphatic polyhydroxy compound and (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates which are reaction products between a (meth)acrylate having a hydroxyl group and a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group which are reaction products between a (meth)acrylate having a hydroxyl group and an acid anhydride.

[0089] Here, examples of the aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the (meth)acrylates 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 isocyanates 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, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

[0090] Specific examples of the compound having two or more (meth)acryloyl groups include, for example, ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol fluorene di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxy, Examples of the monomer include dipropyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and urethane (meth)acrylate compounds.

[0091] Among the compounds having two or more (meth)acryloyl groups, polyfunctional (meth)acrylates are preferred, and polyfunctional (meth)acrylates having 3 to 10 (meth)acryloyl groups are more preferred. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred.

[0092] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, a urea structure, etc. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc.

[0093] The lower limit of the content of the polymerizable compound [E] in the total solid content of the composition (I) is preferably 5 mass%, more preferably 10 mass%, and even more preferably 20 mass%, while the upper limit of this content is preferably 60 mass%, more preferably 50 mass%, and even more preferably 40 mass%.

[0094] ([F] Polymerization initiator) The composition (I) preferably contains a polymerization initiator [F]. Examples of the polymerization initiator [F] include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred. This allows the composition (I) to be photosensitive (radiation sensitive). The photopolymerization initiator refers to a compound that generates active species capable of initiating polymerization of the polymerizable compound [E] and the like when exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. The polymerization initiator [F] can be used alone or in combination of two or more kinds.

[0095] [F] Examples of the polymerization initiator 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, imide sulfonate compounds, onium salt compounds, etc. Among these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds are preferred, and O-acyloxime compounds are more preferred.

[0096] 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.

[0097] Examples of acetophenone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

[0098] 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.

[0099] In addition, when a biimidazole compound is used, it is preferable to use a hydrogen donor in combination in order to improve the sensitivity. The "hydrogen donor" referred to here means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and amine hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

[0100] Examples of the triazine-based compound include the compounds described in JP-B-57-6096 and JP-A-2003-238898, paragraphs

[0063] to

[0065] .

[0101] Examples of O-acyloxime compounds include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (both manufactured by ADEKA CORPORATION), OXE-03, OXE-04 (both manufactured by BASF), and the like can also be used.

[0102] When using a photopolymerization initiator, a sensitizer can be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0103] The lower limit of the content of the polymerization initiator [F] in the total solid content of the composition (I) is preferably 1 mass %, more preferably 3 mass %, while the upper limit of this content is preferably 30 mass %, more preferably 10 mass %.

[0104] (Other organic dyes) The composition (I) may contain a known organic dye other than the organic dye as the phthalocyanine compound [A1] and the copper compound as the infrared shielding agent [B]. Other organic dyes include diiminium compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quaterrylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexaphyrin compounds, etc. (excluding those containing copper atoms). In addition, phthalocyanine compounds other than the phthalocyanine compound [A1] and the phthalocyanine compound as the infrared shielding agent [B] can also be used.

[0105] In addition, it is preferable to use the [A1] phthalocyanine compound in combination with a phthalocyanine compound other than the [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, more preferably 800 nm, and 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 this difference is preferably 100 nm, more preferably 80 nm, and even more preferably 60 nm. The [a] phthalocyanine compound can be any of various conventionally known phthalocyanine compounds.

[0106] The lower limit of the content of the phthalocyanine compound [A1] in the total organic dye in the composition (I) is preferably 50% by mass, more preferably 70% by mass, more preferably 80% by mass, more preferably 90% by mass, and more preferably 99% by mass. It may be preferable to substantially contain only the phthalocyanine compound [A1] as the organic dye. The composition (I) can increase productivity by reducing the content of other organic dyes in this way.

[0107] (Additives) The composition (I) may contain various additives, if necessary, in addition to the above-mentioned components [A1] to [F] and other organic dyes.

[0108] Examples of the additives include surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, residue improvers, developability improvers, and reaction regulators.

[0109] Examples of the surfactant include a fluorine surfactant and a silicone surfactant.

[0110] Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0111] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. The content of the antioxidant can be generally 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phthalocyanine compound [A].

[0112] Examples of the ultraviolet absorber include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones.

[0113] The anti-aggregating agent may include sodium polyacrylate.

[0114] Examples of the residue improving agent include malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol.

[0115] Examples of the developability improver include mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono(meth)acrylate, and the like.

[0116] The reaction regulator may include polyfunctional thiols.

[0117] The lower limit of the content of the components other than the above-mentioned [A1] to [F] components and other organic dyes in the total solid content of the composition (I) is preferably 0.1 mass %, more preferably 1 mass %, while the upper limit of this content is preferably 10 mass %, more preferably 5 mass %.

[0118] (solvent) The composition (I) is usually prepared as a liquid composition containing a solvent (dispersion medium). Any solvent can be appropriately selected and used as long as it disperses or dissolves other components, does not react with these components, and has appropriate volatility.

[0119] Such a solvent is, for example, (poly)alkylene glycol monoalkyl ethers such as 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 and tripropylene 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, (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 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; ketones such as chain ketones, such as methyl ethyl ketone, 2-heptanone, and 3-heptanone, and cyclic ketones, such as cyclopentanone and cyclohexanone; Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate; Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate; Other esters such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, 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 or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone etc. can be mentioned.

[0120] The content of the solvent in the composition (I) is not particularly limited. The lower limit of the solid content concentration (total concentration of each component excluding 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 solid content concentration is preferably 50% by mass, more preferably 40% by mass. By setting the solid content concentration in the above range, the dispersibility, stability, coatability, etc. are improved.

[0121] (Preparation method) The method for preparing the composition (I) is not particularly limited, and the composition can be prepared by mixing each component. For example, when the composition contains a metal oxide as an infrared shielding agent [C] and a dispersing agent [D], a method can be adopted in which a dispersion containing the infrared shielding agent [C], the dispersing agent [D] and a solvent is first prepared, and the phthalocyanine compound [A1], the binder resin [B], and other components as necessary are added to the dispersion, and then mixed. The dispersion or the composition (I) can be filtered as necessary to remove aggregates.

[0122] <Composition for optical sensor (II)> Composition (II) for optical sensors according to one embodiment of the present invention (hereinafter also simply referred to as "composition (II)") contains a phthalocyanine compound [A2]. The phthalocyanine compound [A2] is a compound represented by the following formula (2). Since composition (II) contains such a phthalocyanine compound [A2], it is possible to form an optical filter having few defects such as foreign matter and having good properties in terms of visible light transmittance and infrared shielding properties.

[0123] [ka]

[0124] In formula (2), each of the R's is independently an alkyl group having a substituent, or an aryl group having a substituent. Each of the X's is independently a hydrogen atom, a halogen atom, or an alkyl group. Each of the X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the n's is independently an integer of 3 to 6.

[0125] The phthalocyanine compound [A2] is the same as the phthalocyanine compound [A1] described above, except that the R's are each independently an alkyl group having a substituent or an aryl group having a substituent. The preferred form of the phthalocyanine compound [A2] is also the same as the phthalocyanine compound [A1] described above.

[0126] The composition (II) is the same as the above-mentioned composition (I) except that it contains the phthalocyanine compound [A2] instead of the phthalocyanine compound [A1] and does not contain the binder resin [B] as an essential component. The composition (II) preferably contains the binder resin [B]. Other specific and preferred forms of the composition (II) are the same as those of the above-mentioned composition (I).

[0127] <Infrared shielding film> From the composition (I) and the composition (II) according to one embodiment of the present invention (hereinafter, the compositions (I) and (II) are also collectively referred to simply as the "compositions"), an infrared shielding film for an optical filter can be formed. This infrared shielding film has few defects such as foreign matter and has good properties with respect to visible light transmittance and infrared shielding properties.

[0128] The infrared shielding film can be formed, for example, by the following method. First, the composition is applied onto a support, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film is exposed to light, and then developed using a developer to dissolve and remove the non-exposed portion of the coating film. Then, post-baking is performed to obtain an infrared shielding film (I) patterned into a predetermined shape. Note that, when the composition does not contain the polymerizable compound [E] and the polymerization initiator [F], it is not necessary to perform a curing treatment such as exposure. Also, it is not necessary to perform a development treatment, and in this case, it is possible to form an infrared shielding film that is not patterned.

[0129] The support to which the composition is applied corresponds to the transparent substrate, microlens, color filter, etc. The application can be performed by any suitable application method such as spraying, roll coating, rotary coating (spin coating), slit die coating (slit coating), bar coating, etc.

[0130] The conditions for the heat drying in the pre-baking are, for example, 70° C. or higher and 110° C. or lower, and about 1 minute or higher and 10 minutes or lower.

[0131] Examples of the radiation source used for exposing the coating film include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, and laser light sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. Ultraviolet LEDs can also be used as the exposure light source. The wavelength of the radiation is preferably in the range of 190 nm to 450 nm. The radiation exposure dose is generally 10 J / m 2 More than 50,000J / m 2 It is about the following.

[0132] The developer is generally an alkaline developer. As the alkaline developer, for example, an aqueous solution of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added to the alkaline developer. After development, the film is usually washed with water.

[0133] The developing method may be a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid puddle) developing method, etc. The developing conditions are about 5 seconds or more and 300 seconds or less at room temperature.

[0134] The post-baking conditions are usually 180° C. to 280° C. and 1 minute to 60 minutes.

[0135] The lower limit of the average thickness of the infrared shielding film thus formed is usually 0.5 μm, preferably 1 μm. Meanwhile, the upper limit of this average thickness is usually 10 μm, preferably 5 μm. By having the average thickness of the infrared shielding film within the above range, a better balance between visible light transmittance and infrared shielding properties can be achieved.

[0136] <Optical filters> The infrared shielding film formed from the composition according to one embodiment of the present invention can be used for an optical filter. The optical filter having the infrared shielding film has few defects such as foreign matter and has good properties regarding visible light transmittance and infrared shielding. The optical filter is used as an optical filter for an optical sensor such as a solid-state image sensor.

[0137] The optical filter may be composed of only the infrared shielding film, or may be composed of the infrared shielding film and other components. For example, the optical filter may be a laminate having the infrared shielding film and other layers.

[0138] The infrared shielding film is preferably incorporated as one component in an optical sensor such as a solid-state imaging device. In this case, the infrared shielding film functions as an optical filter (infrared cut filter) by itself. By incorporating the infrared shielding film in an optical sensor, it is possible to obtain a large process margin, which is preferable. When the infrared shielding film is incorporated in a solid-state imaging device, the infrared shielding film can be disposed, for example, on the outer surface side of a microlens of the solid-state imaging device, between a microlens and a color filter, or between a color filter and a photodiode. The infrared shielding film is preferably laminated between a microlens and a color filter or between a color filter and a photodiode.

[0139] The optical filter may be one in which the infrared shielding film is laminated on the surface of a transparent substrate. The transparent substrate may be made of glass or a transparent resin. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Such an optical filter is also suitably used as an infrared cut filter in a solid-state imaging device.

[0140] Optical sensors such as solid-state imaging devices equipped with the above optical filters are useful in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, car cameras, personal digital assistants, personal computers, video games, medical equipment, and the like.

[0141] <Optical sensor> The optical filter is used in optical sensors such as solid-state imaging devices. The optical filter has few defects such as foreign matter and has good properties in terms of visible light transmittance and infrared shielding properties, so that optical sensors such as solid-state imaging devices having the optical filter have high sensitivity, color reproducibility, and other properties, and are excellent in practical use.

[0142] Hereinafter, a solid-state imaging element will be described as an example of an optical sensor. The solid-state imaging element generally has a structure in which a layer in which a plurality of photodiodes are arranged, a color filter, and a microlens are laminated in this order. A planarization layer may be provided between these layers. In the solid-state imaging element, light is incident from the microlens side. The incident light passes through the microlens and the color filter and reaches the photodiode. The color filters are configured such that only light in a specific wavelength range passes through each of the R (red), G (green), and B (blue) filters, for example.

[0143] In the solid-state imaging device, the optical filter (infrared shielding film) can be provided on the outer surface side of the microlens, between the microlens and the color filter, between the color filter and the layer in which the multiple photodiodes are arranged, etc. The optical filter is preferably laminated between the microlens and the color filter or between the color filter and the photodiode. Note that another layer (such as a planarization layer) may be provided between the optical filter and the microlens, color filter, photodiode, etc.

[0144] Specific examples of the solid-state imaging element include CCD and CMOS as camera modules, etc. The solid-state imaging element is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, car cameras, personal digital assistants, personal computers, video games, medical equipment, etc. EXAMPLES

[0145] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0146] <Synthesis Example 1> Synthesis of phthalocyanine compound (a-1) 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline, 4.76 g of vanadium trichloride, and 13.74 g of DBU were stirred in 100 mL of 1-pentanol at an internal temperature of 125° C. for 24 hours. Then, 600 mL of methanol was added, and the precipitate was collected by filtration and dried. The product was purified by column chromatography (silica gel / toluene) to obtain 11.2 g of a green powder. The obtained compound was confirmed to be the target compound (a-1) represented by the following formula (a-1) from the following analytical results. MS: (EI) m / z 2245M+ Elemental analysis: Measured value (C: 68.44%, H: 6.44%, N: 4.99%); Theoretical value (C: 68.47%, H: 6.46%, N: 4.99%) The toluene solution of the compound thus obtained exhibited a maximum absorption at 734.5 nm and a gram absorption coefficient of 6.75 × 10 4 The concentration was mL / g cm.

[0147] [ka] In the above formula, "*" indicates a bond (the same applies to the following chemical formulae).

[0148] <Synthesis Example 2> Synthesis of phthalocyanine compound (a-2) A green powder (14.5 g) was obtained in the same manner as in Synthesis Example 1, except that 18.6 g of 4,7-bis(4-methoxybutyl)-1,3-diiminoisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1. The obtained compound was confirmed to be the target compound (a-2) represented by the following formula (a-2) based on the following analytical results. MS: (EI) m / z 1267M+ Elemental analysis: Measured value (C: 68.20%, H: 7.66%, N: 8.82%); Theoretical value (C: 68.17%, H: 7.63%, N: 8.83%) The toluene solution of the compound thus obtained exhibited a maximum absorption at 734.0 nm and a gram absorption coefficient of 1.21 × 10 5 The concentration was mL / g cm.

[0149] [ka]

[0150] <Synthesis Example 3> Synthesis of phthalocyanine compound (a-3) 5.9 g of a green powder was obtained in the same manner as in Synthesis Example 1, except that 29.4 g of 4,7-bis(4-(3-methoxyphenoxy)butyl)-1,3-diiminoisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1. The obtained compound was confirmed to be the target compound (a-3) represented by the following formula (a-3) from the following analytical results. MS: (EI) m / z 2003M+ Elemental analysis: Measured value (C: 71.85%, H: 6.44%, N: 5.57%); Theoretical value (C: 71.87%, H: 6.43%, N: 5.59%) The toluene solution of the compound thus obtained exhibited a maximum absorption at 735.5 nm and a gram absorption coefficient of 7.40 × 10 4 The concentration was mL / g cm.

[0151] [ka]

[0152] <Synthesis Example 4> Synthesis of phthalocyanine compound (a-4) A green powder (11.2 g) was obtained in the same manner as in Synthesis Example 1, except that 28.0 g of 4,7-bis(4-(2-fluorophenoxy)butyl)-1,3-diiminoisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1. The obtained compound was confirmed to be the target compound (a-4) represented by the following formula (a-4) based on the following analytical results. MS: (EI) m / z 1908M+ Elemental analysis: Measured value (C: 70.49%, H: 5.51%, N: 5.85%); Theoretical value (C: 70.47%, H: 5.49%, N: 5.87%) The toluene solution of the compound thus obtained exhibited a maximum absorption at 735.5 nm and a gram absorption coefficient of 7.89 × 10 4 The concentration was mL / g cm.

[0153] [ka]

[0154] <Synthesis Example 5> Synthesis of phthalocyanine compound (a-5) 31.0 g of a green powder was obtained in the same manner as in Synthesis Example 1, except that 38.8 g of 4,7-bis(4-((1,6-dimethoxynaphthalen-2-yl)oxy)butyl)-1,3-diiminoisoindoline was used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1. The obtained compound was confirmed to be the target compound (a-5) represented by the following formula (a-5) based on the following analytical results. MS: (EI) m / z 2645M+ Elemental analysis: Measured value (C: 72.62%, H: 6.05%, N: 4.30%); Theoretical value (C: 72.63%, H: 6.10%, N: 4.23%) The toluene solution of the compound thus obtained exhibited a maximum absorption at 735.5 nm and a gram absorption coefficient of 5.85 × 10 4 The concentration was mL / g cm.

[0155] [ka]

[0156] <Synthesis Example 6> Synthesis of phthalocyanine compound (a-6) 28.1 g of a green powder was obtained in the same manner as in Synthesis Example 1, except that 19.4 g of 4,7-bis(4-((1,6-dimethoxynaphthalen-2-yl)oxy)butyl)-1,3-diiminoisoindoline and 16.5 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline were used instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1. The compound obtained was confirmed to be the target compound (a-6) represented by the following formula (a-6) by LC-MS, based on the agreement of m / z of each component. The toluene solution of the compound thus obtained exhibited a maximum absorption at 735.5 nm and a gram absorption coefficient of 6.30 × 10 4 The concentration was mL / g cm.

[0157] [ka]

[0158] The above phthalocyanine compounds (a-1) to (a-6) are all phthalocyanine compounds represented by the above formula (1).

[0159] <Synthesis Example 7> Synthesis of phthalocyanine compound (a'-1) In accordance with the description in Example (65) of JP-A-02-138382, a phthalocyanine (a'-1) (maximum absorption wavelength 725 nm) for comparative examples represented by the following formula was synthesized.

[0160] [ka]

[0161] <Synthesis Example 8> Synthesis of phthalocyanine compound (a'-2) A phthalocyanine compound (a'-2) (maximum absorption wavelength 728 nm) for comparative examples represented by the following formula was synthesized using the method described in paragraph

[0075] (Example 4) of JP2016-204536A.

[0162] [ka]

[0163] <Synthesis Example 9> Synthesis of phthalocyanine compound (a'-3) Using the method described in paragraphs

[0020] to

[0025] (Example 1) of JP-A-05-25177, a phthalocyanine compound (a'-3) (maximum absorption wavelength 692 nm) for other dyes represented by the following formula was synthesized.

[0164] [ka]

[0165] <Synthesis Example 10> Synthesis of cesium tungsten oxide powder Using the method described in paragraph

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

[0166] Synthesis Example 11: Synthesis of binder resin (b-1) 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 methacrylic acid were dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate, and 3 parts by mass of 2,2'-azoisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were further added. After purging the reaction vessel with nitrogen, the mixture was heated at 80°C for 5 hours while stirring and bubbling with nitrogen to obtain a solution containing binder resin (b-1) (binder resin solution (B-1): solid content concentration 35% by mass). The molecular weight of the obtained binder resin (b-1) was measured in terms of polystyrene using a gel permeation chromatography (GPC) apparatus (GPC-104 type, column: Showa Denko LF-604 x 3 and KF-602 x 3, developing solvent: tetrahydrofuran) and the weight average molecular weight (Mw) was 9700, the number average molecular weight (Mn) was 5700, and Mw / Mn was 1.70. In this synthesis example, the charge ratio (mass ratio) of each monomer and the content ratio (mass ratio) of the structural units derived from each monomer in the obtained binder resin can be considered to be substantially the same (the same applies to the following synthesis example 14).

[0167] Synthesis Example 12: Synthesis of binder resin (b-2) A flask equipped with a cooling tube and a stirrer was charged with 200 parts by mass of propylene glycol monomethyl ether, 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 dropped over 3 hours, and the temperature was maintained after the dropwise addition to polymerize for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 to 120 ° C., and the reaction was continued for another 2 hours. After cooling, 25 parts by mass of propylene glycol monomethyl ether, 116 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, and a catalytic amount of dimethylbenzylamine were added, and the temperature was raised to 110 ° C. and the reaction was continued for 9 hours to obtain a solution containing a binder resin (b-2) represented by the following formula (binder resin solution (B-2): solid content concentration 40% by mass). When the molecular weight of the obtained binder resin was measured 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 Mw / Mn was 2.16.

[0168] [ka] (In the above formula, the composition ratio is a mass ratio.)

[0169] Synthesis Example 13: Synthesis of binder resin (b-3) A flask equipped with a cooling tube and a stirrer was charged with 200 parts by mass of propylene glycol monomethyl ether, 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 dropped over 3 hours, and the temperature was maintained after the dropwise addition to polymerize for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 to 120 ° C., and the reaction was continued for another 3 hours. After cooling, 28 parts by mass of propylene glycol monomethyl ether, 119 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, and a catalytic amount of dimethylbenzylamine were added, and the temperature was raised to 110 ° C. and the reaction was continued for 30 hours to obtain a solution containing a binder resin (b-3) represented by the following formula (binder resin solution (B-3): solid content concentration 40% by mass). When the molecular weight of the obtained binder resin was measured 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 Mw / Mn was 2.21.

[0170] [ka] (In the above formula, the composition ratio is a mass ratio.)

[0171] Synthesis Example 14: Synthesis of binder resin (b-4) 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 charged, and 32 parts by mass of glycidyl methacrylate, 40 parts by mass of 3-methacryloxypropyltriethoxysilane, 11 parts by mass of benzyl methacrylate, 3 parts by mass of n-butyl methacrylate, and 14 parts by mass of methacrylic acid were charged and substituted with nitrogen. The temperature of the solution was then raised to 80° C. while gently stirring. The solution was polymerized by holding at this temperature for 5 hours to obtain a solution containing a binder resin (b-4) (hereinafter referred to as the binder resin solution (B-4) with a solid content concentration of 35% by mass). The molecular weight of the obtained binder resin was measured in the same manner as in Synthesis Example 11, and the weight average molecular weight (Mw) was 9500, the number average molecular weight (Mn) was 5800, and Mw / Mn was 1.64.

[0172] <Synthesis Example 15> Dispersant (d-2) Using the method described in the literature (Macromolecules 1992, 25, p5907-5913), 45 parts by weight of dimethylaminoethyl methacrylate, 20 parts by weight of 2-ethylhexyl methacrylate, 5 parts by weight of n-butyl methacrylate, PME-200 (methoxypolyethylene glycol monomethacrylate, and CH2=C(CH3)COO(C2H4O) n 30 parts by mass of a polymer of a monomer represented by -CH3 (n≒4) was polymerized in one batch to obtain a reaction solution containing a random copolymer. The reaction solution was then quenched with methanol, and the resulting reaction solution was washed with a 7% by mass aqueous solution of sodium bicarbonate and then with water. After this, the solvent was replaced with propylene glycol monomethyl ether acetate (PGMEA) to obtain a dispersant solution (D-2) containing a dispersant (d-2) with a yield of 80% by mass. The amine value of the resulting dispersant (d-2) was 160 mgKOH / g, Mw was 9500, Mw / Mn was 1.21, and the solid content of the dispersant solution (D-2) was 39.6% by mass.

[0173] [Preparation Example 1] Preparation of Dispersion (C-1) 25.00 parts by mass of the above cesium tungsten oxide, 13.30 parts by mass of BYK-LPN6919 (solid content concentration 60% by mass, amine value 120 mgKOH / g) from BYK-Chemie as a dispersant (d-1), and 61.70 parts by mass of cyclopentanone (CPN) as a solvent (dispersion medium) were prepared. These were filled into a container together with 2000 parts by mass of zirconia beads having a diameter of 0.1 mm, and dispersed with a paint shaker to obtain a dispersion liquid (C-1) having an average particle diameter (D50) of 19 nm. The average particle diameter was measured by DLS method using a light scattering measuring device (ALV's "ALV-5000" from Germany).

[0174] [Preparation Example 2] Preparation of Dispersion (C-2) A dispersion (C-2) having an average particle size of 19 nm was obtained in the same manner as in Preparation Example 1, except that the dispersant solution (D-2) was changed to 20.20 parts by mass and the solvent was changed to 54.80 parts by mass of CPN.

[0175] [Preparation Example 3] Preparation of dye solutions (A-1) to (A-9) 5.00 parts by mass of the phthalocyanine compound (a-1) and 95.00 parts by mass of CPN as a solvent were weighed into a container and mixed with a stirrer. The resulting solution was filtered under a constant pressure of 0.05 MPa using a 0.2 μm polytetrafluoroethylene (PTFE) filter to obtain a dye solution (A-1). In addition, the dye solutions (A-2) to (A-6), (A-8) and (A-9) shown in Table 1 were obtained in the same manner as above, except that the phthalocyanine compounds (a-2) to (a-6), (a-8) and (a-9) were used as the phthalocyanine compounds, respectively. The dye solution (A-7) was prepared in the same manner, except that 4.50 parts by mass of the phthalocyanine compound (a-1), 1.20 parts by mass of the phthalocyanine compound (a'-3), and 94.30 parts by mass of CPN as the solvent were used.

[0176] [Example 1] 20.00 parts by mass of the dispersion (C-1), 23.15 parts by mass of the dye solution (A-1), 21.01 parts by mass of the binder resin solution (B-1), 8.14 parts by mass of "KAYARAD DPHA" (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) from Nippon Kayaku Co., Ltd. as a polymerizable compound, 1.53 parts by mass of "NCI-930" (O-acyloxime compound) from ADEKA Co., Ltd. as a polymerization initiator, 0.05 parts by mass of "FTX-218D" (fluorine-based surfactant) from Neos Co., Ltd. as a surfactant, 0.31 parts by mass of "Karens MT PE1" (multifunctional thiol) from Showa Denko Co., Ltd. as a reaction adjuster, 0.10 parts by mass of "Irganox1010" (phenol-based antioxidant) from BASF Co., Ltd. as an antioxidant, and 25.71 parts by mass of cyclopentanone (CNP) as a solvent were weighed into a container and mixed with a stirrer. About 100 mL of this mixture was pressure filtered using a 0.5 μm PTFE filter at a constant pressure of 0.05 MPa to obtain the composition of Example 1.

[0177] [Examples 2 to 13, Comparative Examples 1 to 3] The compositions of Examples 2 to 13 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that the types and amounts (parts by mass) of the dispersion liquid, dye solution, and binder resin solution, as well as the amounts (parts by mass) of the polymerizable compound, polymerization initiator, surfactant, reaction regulator, antioxidant, and solvent were as shown in Table 1. Table 1 also shows the types and amounts in the solid content of [A] the phthalocyanine compound, [B] the binder resin, [C] the infrared shielding agent, [D] the dispersant, and other dyes in each obtained composition. "CsWO" in Table 1 stands for cesium tungsten oxide (Cs 0.33 WO3).

[0178] [evaluation] The following evaluations were carried out using each of the obtained compositions. The evaluation results are shown in Table 1.

[0179] Each composition was applied to a glass substrate by spin coating to a predetermined thickness, and then the coating was heated at 100°C for 120 seconds and irradiated with 500 mJ / cm using an i-line stepper. 2Then, the substrate was heated at 220°C for 300 seconds to prepare an infrared shielding film having an average film thickness of 2.0 to 4.0 μm on the glass substrate. The average film thicknesses are shown in Table 1. The film thicknesses were measured using a stylus step gauge (Yamato Scientific Co., Ltd.'s "Alpha Step IQ"). Next, the transmittance in each wavelength region of the infrared shielding film prepared on the glass substrate was measured relative to the glass substrate using a spectrophotometer (JASCO Corp.'s "V-7300"). From the obtained spectrum, evaluation was performed according to the following evaluation criteria.

[0180] (Visible light transparency) The average transmittance from 430 to 580 nm was calculated. If the average transmittance is less than 70%, the sensitivity decreases when used as an infrared shielding film. The average transmittance was evaluated according to the following criteria. A: 80% or more B: 70% or more but less than 80% C: Less than 70%

[0181] (visible transmission window range) The range in which the transmittance in the range of 430-580 nm is continuously 70% or more was determined. When the range in which the transmittance is continuously 70% or more is 175 nm or more, it is assumed that the film has high sensitivity and is highly practical when used as an infrared shielding film. The visible light transmission window range was evaluated according to the following criteria. A:200nm or more B: 175nm or more and less than 200nm C: Less than 175 nm

[0182] (Infrared shielding range) The range in which the transmittance in the range of 700-800 nm was continuously 20% or less was determined. When the range in which the transmittance was continuously 20% or less was 20 nm or more, it was estimated that the film had high noise shielding function and was highly practical when used as an infrared shielding film. The infrared shielding range was also evaluated according to the following criteria. A: 30nm or more B: 20nm or more and less than 30nm C: Less than 20 nm

[0183] (Average Off-Slope) In the range of 500-750nm, the longest wavelength where the transmittance is 80% or more is defined as (X), and the shortest wavelength where the transmittance is 20% or less is defined as (Y), and the average off-slope (Z) was calculated using the following formula. When the average off-slope is 0.45 or more, it is possible to improve the color reproducibility of the image obtained and the noise shielding function when used as an infrared shielding film, and it is estimated to be highly practical. In addition, the average off-slope was evaluated according to the following criteria. (Z)=60 / ((Y)-(X)) AA: 0.60 or higher A: 0.50 or more and less than 0.60 B: 0.45 or more and less than 0.50 C: Less than 0.45

[0184] (Heat resistance) The infrared shielding film prepared on the glass substrate 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 relative to the glass substrate using a spectrophotometer (JASCO Corporation's "V-7300"). At this time, the absorbance at the wavelength at which the transmittance of the prepared infrared shielding film is the lowest in the range of 700-800 nm is (A1), the absorbance at the same wavelength after heating at 260°C is (A2), and the absorbance retention rate = 100 x (A1) / (A2), and the heat resistance at 260°C was evaluated according to the following criteria. When the retention rate is 30% or more, it is possible to maintain high heat resistance when used as an infrared shielding film by combining it with a protective film, etc., and it is estimated to be highly practical. In addition, the retention rate was evaluated according to the following criteria. AA: 90% or more A: 60% to less than 90% B: 30% or more but less than 60% C: Less than 30%

[0185] (Defect suppression) Each composition was applied onto a silicon substrate by spin coating, and the coating was cured to form a cured film with a thickness of approximately 1 μm. The defect density of the cured film was measured using a defect / foreign matter inspection device (KLA-Tencor's "KLA 2351"). It can be determined that the smaller the defect density value, the higher the defect suppression ability. Note that a defect refers to a detection point with a size of 1 μm or more. Based on the above defect density, the defect suppression ability was evaluated according to the following criteria. A:10 / cm 2 below B:10 / cm 2 Super 50 / cm 2 below C:50 / cm 2 Super

[0186] (PCD stability) Each composition was applied onto a silicon substrate by spin coating, and a coating film with a thickness of about 1 μm was formed without curing the coating film. The defect density of the coating film was measured using a defect / foreign matter inspection device (KLA-Tencor's "KLA 2351"). Next, the defect density of the coating film was measured at regular intervals, and the time when the number of defects increased by 20% or more from the initial value was measured, and the post-coating delay (PCD) stability after coating was evaluated according to the following criteria. It is estimated that the higher the PCD stability value, the higher the practicality. A: More than 24 hours B: 12 ​​hours or more but less than 24 hours C: Less than 12 hours

[0187] [Table 1]

[0188] As shown in Table 1 above, all of Examples 1 to 13 were evaluated as being good in terms of visible light transmittance, visible light transmission window range, infrared shielding range, average off-slope, heat resistance, defect suppression, and PCD stability. Among the Examples using the phthalocyanine compound represented by the above formula (1), Examples 1, 3 to 6 using phthalocyanine compounds (a-1, a-3 to a-6) in which R has a substituent have higher heat resistance than Example 2 using phthalocyanine compound (a-2) in which R does not have a substituent. In addition, it can be seen that, among the above Examples using phthalocyanine compounds in which R has a substituent, Examples 1, 3, and 4 also have good visible light transmittance. [Industrial Applicability]

[0189] The composition for optical sensors of the present invention can be suitably used as a material for forming an optical filter of an optical sensor such as a solid-state imaging device.

Claims

1. A phthalocyanine compound represented by the following formula (1), and Binder resin having a (meth)acryloyl group A composition for optical sensors comprising: 【Chemistry 1】 (In formula (1), each of the multiple R's is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Each of the multiple X's is independently a hydrogen atom, a halogen atom, or an alkyl group. The multiple X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the multiple n's is independently an integer of 3 to 6.)

2. A phthalocyanine compound represented by the following formula (1), and Binder resin with a ring structure in the main chain Contains The composition for optical sensors, wherein the binder resin has a structural unit derived from an N-substituted maleimide monomer. 【Chemistry 2】 (In formula (1), each of the multiple R's is independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Each of the multiple X's is independently a hydrogen atom, a halogen atom, or an alkyl group. The multiple X's may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom. Each of the multiple n's is independently an integer of 3 to 6.)

3. 3. The composition for optical sensors according to claim 1, wherein each of the plurality of R's is independently an alkyl group having a substituent or an aryl group having a substituent.

4. 4. The composition for optical sensors according to claim 1, wherein the alkyl group and the aryl group each represented by the plurality of R have a substituent, which is a group having a heteroatom.

5. 5. The composition for optical sensors according to claim 4, wherein the substituent is a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, or a combination thereof.

6. Infrared shielding agents which are metal oxides, copper compounds (excluding the above-mentioned phthalocyanine compounds), or combinations thereof The composition for optical sensors according to claim 1 , further comprising:

7. 7. The optical sensor composition of claim 6, wherein the metal oxide is cesium tungsten oxide.

Images