CN112789526A

CN112789526A - Composition for optical sensor

Info

Publication number: CN112789526A
Application number: CN201980064495.5A
Authority: CN
Inventors: 畠山耕治; 村田裕亮; 川部泰典; 和田浩平
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2018-10-05
Filing date: 2019-10-03
Publication date: 2021-05-11
Anticipated expiration: 2039-10-03
Also published as: TWI803701B; CN116520638A; JP2024020454A; TW202022050A; JP7424300B2; JPWO2020071486A1; CN112789526B; CN116520637A; KR20210071971A; WO2020071486A1

Abstract

Provided is a composition for an optical sensor, which can form an optical filter for an optical sensor having excellent characteristics regarding visible light transmittance and infrared shielding properties. The present invention is a composition for an optical sensor, comprising a phthalocyanine compound represented by the following formula (1) and a binder resin. In the formula (1), each of R is independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. And X's are each independently a hydrogen atom, a halogen atom or an alkyl group. Multiple xs may also be bonded to each other and together with the bonded carbon chains 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 of 3 to 6.

Description

Composition for optical sensor

Technical Field

The present invention relates to a composition for an optical sensor.

Background

A solid-state imaging element as an optical sensor is mounted in a video camera, a digital camera, a mobile phone with a camera function, and the like. As a solid-state imaging device, specifically, a Charge-coupled device (CCD) image sensor, a Complementary Metal Oxide Semiconductor (CMOS) image sensor, or the like is known. The sensitivity of the photodiode provided in these solid-state imaging devices ranges from the visible light region to the infrared region. Therefore, a filter for cutting off infrared rays is provided in the solid-state imaging element. The sensitivity of the solid-state imaging device can be corrected so as to approach the visual acuity of a human being by the optical filter (infrared ray cut filter). In optical sensors other than the solid-state imaging device, a filter for blocking infrared rays may be similarly provided.

The optical filter contains a pigment or a coloring matter as an infrared ray shielding agent. The infrared shielding agent is required to have properties of sufficiently transmitting visible light and absorbing infrared light. As one of the infrared shielding agents, particularly as a good shielding agent for near infrared rays, use of a phthalocyanine compound has been studied (see japanese patent laid-open No. 2008-201952).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2008-201952

Disclosure of Invention

Problems to be solved by the invention

However, in a conventional optical filter using a phthalocyanine compound, defects such as foreign substances may occur due to the influence of compatibility and the like. Such defects may affect the visible light transmittance, infrared shielding property, and the like of the optical filter. In addition, when an infrared shielding film of an optical filter is formed by applying a composition containing a coloring matter such as a phthalocyanine compound, if the film is left for a long time after application, defects such as foreign matters are likely to occur in the obtained infrared shielding film. In the production process, it is desired that an infrared shielding film with few defects such as foreign matters can be obtained even if it is left to harden for a while after coating.

Further, conventional optical filters have not been sufficiently satisfactory with respect to visible light transmittance and infrared shielding properties. Specifically, when an optical filter is used as an infrared ray blocking filter of an optical sensor such as a solid-state image pickup device, it is required that not only is the visible light transmittance high and the infrared ray transmittance low, but also a wavelength region having a high visible light transmittance, a wavelength region having a low infrared ray transmittance wide and a wavelength region having a high visible light transmittance are close to a wavelength region having a low infrared ray transmittance. When the optical filter having the above characteristics is used for an optical sensor such as a solid-state imaging element, sensitivity, a noise shielding function, color reproducibility, and the like can be improved.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition for an optical sensor, which can form an optical filter for an optical sensor having few defects such as foreign substances and having good characteristics regarding visible light transmittance and infrared shielding property.

Means for solving the problems

The invention made to solve the above problems is a composition for an optical sensor, comprising a phthalocyanine compound represented by the following formula (1) and a binder resin.

[ solution 1]

(in the formula (1), R is respectively and independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, X is respectively and independently a hydrogen atom, a halogen atom or an alkyl group, X can also be mutually bonded 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, n is respectively and independently an integer of 3-6.)

Another invention made to solve the above problems is a composition for an optical sensor, which contains a phthalocyanine compound represented by the following formula (2).

[ solution 2]

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a composition for an optical sensor which can form an optical filter for an optical sensor having few defects such as foreign matter and having good characteristics with respect to visible light transmittance and infrared shielding property.

Detailed Description

Hereinafter, the optical sensor composition according to one embodiment of the present invention will be described in detail.

< composition for optical sensor (I) >

The composition (I) for an optical sensor according to one embodiment of the present invention (hereinafter, also simply referred to as "composition (I)") contains [ a1] phthalocyanine compound and [ B ] binder resin. The composition preferably further contains [ C ] an infrared shielding agent which is a metal oxide, a copper compound (excluding [ A ] phthalocyanine compound), or a combination thereof.

([ A1] phthalocyanine compound)

[A1] The phthalocyanine compound is a compound represented by the following formula (1). [A1] The phthalocyanine compound has high transmittance in the visible light region (for example, a wavelength region of 430nm to 580 nm), and high shielding property in the near infrared region (for example, a wavelength region of 700nm to 800 nm). Further, [ A1] the phthalocyanine compound has excellent compatibility with other components. The composition (I) contains the [ A1] phthalocyanine compound, and thus can form an optical filter having few defects such as foreign substances and having good characteristics with respect to visible light transmittance and infrared shielding properties.

[ solution 3]

In the formula (1), each of R is independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. And X's are each independently a hydrogen atom, a halogen atom or an alkyl group. Multiple xs may also be bonded to each other and together with the bonded carbon chains 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 of 3 to 6.

Examples of the alkyl group represented by R include: a straight-chain or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a tert-butyl group. The upper limit of the number of carbon atoms of the alkyl group is preferably 12, more preferably 8, and still more preferably 4.

Examples of the aryl group represented by R include a monovalent group including only an aromatic ring and a monovalent group in which an alkyl group is bonded to an aromatic ring. Specific examples of the aryl group represented by R include: phenyl, tolyl, xylyl, naphthyl, anthracenyl, and the like. The aryl group is preferably a group containing only an aromatic ring, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group in terms of visible light transmittance and the like.

The R is preferably a substituted or unsubstituted aryl group in terms of heat resistance and the like of the optical filter obtained.

The alkyl group and the aryl group represented by each of the R groups may have a substituent or may not have a substituent, but preferably have a substituent. That is, the plurality of R are preferably each independently an alkyl group having a substituent or an aryl group having a substituent. Thus, by having a substituent at each of the plurality of R groups, the compatibility of the [ a1] phthalocyanine compound is further improved, defects such as foreign substances in the obtained optical filter are further suppressed, and the characteristics relating to visible light transmittance and infrared shielding property are further improved. Further, the optical filter obtained by having a substituent at a plurality of R groups also has improved heat resistance.

The substituent that the alkyl group and the aryl group represented by each of the R groups may have may be a hydrocarbon group such as an alkenyl group or an alkynyl group, but is preferably a group having a hetero atom. The heteroatom means an atom other than a hydrogen atom and a carbon atom. When the alkyl group and the aryl group represented by each of the R groups contain a substituent having a hetero atom, compatibility and the like are further improved, defects such as foreign substances in the obtained optical filter are further suppressed, and characteristics relating to visible light transmittance and infrared shielding property are further improved. Further, when the plurality of R groups contain a substituent having a hetero atom, the heat resistance of the obtained optical filter is also improved. The hetero atom is preferably a halogen atom, an oxygen atom or a sulfur atom, and more preferably a halogen atom or an oxygen atom.

As the substituent having a hetero atom, there may be mentioned: halogen atom, alkoxy group, alkylthio group, cyano group, nitro group, carboxyl group, hydroxyl group, thiol group, amino group, etc.

Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, etc., preferably fluorine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group, and a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

The alkylthio group includes a methylthio group (CH)₃-S-), ethylthio (C)₂H₅-S-), propylthio (C)₃H₇-S-) and the like, more preferably methylthio and ethylthio.

Among the substituents having a hetero atom, a halogen atom, an alkoxy group and an alkylthio group are preferable, and a halogen atom and an alkoxy group are more preferable. Further, a halogen atom, methoxy group, ethoxy group, methylthio group, ethylthio group, or a combination thereof is also preferable.

The plurality of R's may be the same or different, but are preferably the same.

Examples of the halogen atom represented by X include the atoms exemplified as the halogen atom of the substituent.

Examples of the alkyl group represented by X include the alkyl group represented by R.

The plurality of xs may be bonded to each other. In general, two of the xs bonded to the same benzene ring are bonded to each other, and form an aromatic ring together with the bonded carbon chains. Examples of the aromatic ring to be formed include: benzene rings, naphthalene rings, anthracene rings, and the like. The hydrogen atoms of these aromatic rings may also be substituted with hydrocarbon groups or other substituents.

The X is preferably a hydrogen atom. The plural xs may be the same or different, but preferably are the same.

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

Here, the derivative of a metal atom means an atom group containing a metal atom. The trivalent metal atom means a metal atom that can be a trivalent cation. Examples of the trivalent metal atom include Al and In. By tetravalent metal atom is meant a metal capable of being a tetravalent cationA metal atom. Examples of the tetravalent metal atom include Si, Ge, and Sn. Further, the metal atom includes a semimetal atom. As the derivatives of the trivalent or tetravalent metal atom represented by M, there may be mentioned: AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl₂、SiBr₂、SiI₂、Si(OH)₂、GeCl₂、GeBr₂、GeI₂、SnCl₂、SnBr₂、SnI₂、Sn(OH)₂VO, TiO, and the like.

M is preferably H₂(two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl₂AlCl, VO, and TiO, more preferably VO.

The lower limit of n is preferably 4. The upper limit of n is preferably 5, and more preferably 4. The plurality of n may be the same or different, but is preferably the same.

[A1] The lower limit of the maximum absorption wavelength of the phthalocyanine compound is preferably 680nm, more preferably 700nm, and still more preferably 720 nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000nm, more preferably 900nm, still more preferably 800nm, and still more preferably 750 nm. When the maximum absorption wavelength of the [ a1] phthalocyanine compound is in the above range, an optical filter having more excellent characteristics with respect to visible light transmittance and infrared shielding property can be formed.

[A1] The method for synthesizing the phthalocyanine compound is not particularly limited, and known methods may be combined for synthesis. For example, the compound can be synthesized by reacting a phthalonitrile (phthalonitrile) compound represented by the following formula (i) or a1, 3-diiminoisoindoline compound represented by the following formula (ii) with a metal or a metal derivative.

[ solution 4]

In the formulae (i) and (ii), R, X and n are the same as those in the formula (1).

Examples of the metal or metal derivative include: al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, and halides, carboxylates, sulfates, nitrates, carbonyl compounds, oxides, complexes, etc., of these. Among these, halides and carboxylates of metals 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 bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxychloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, lead acetate, indium chloride, titanium chloride, tin chloride, and the like.

The reaction temperature is, for example, 60 ℃ to 300 ℃, preferably 100 ℃ to 220 ℃. The reaction time is, for example, 30 minutes to 72 hours, preferably 1 hour to 48 hours. In the reaction, a solvent is preferably used. The solvent used in the reaction is preferably an organic solvent having a boiling point of 60 ℃ or higher, more preferably 80 ℃ or higher.

Examples of the organic solvent to be used include: alcohol solvents such as 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, and the like, and high boiling point solvents such as dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, 1, 3-dimethyl-2-imidazolidinone (1, 3-dimethyllimidazolidinone, DMI), urea, and the like.

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

In the case of the phthalocyanine compound in which M in the formula (1) is two hydrogen atoms, it can be produced by reacting the phthalonitrile compound represented by the formula (i) or the 1, 3-diiminoisoindoline compound represented by the formula (ii) with sodium or potassium metal under the above-mentioned reaction conditions, and then subjecting the sodium or potassium metal as the central metal to a removal treatment with hydrochloric acid, sulfuric acid or the like.

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

The phthalonitrile compound represented by the formula (i) and the 1, 3-diiminoisoindoline compound represented by the formula (ii) can be synthesized by a known method. For example, the synthesis can be carried out by referring to the method described in Japanese patent laid-open publication No. 2003-516421.

The lower limit of the content of the [ a1] phthalocyanine compound in the total solid components (all components except 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 the content is preferably 30% by mass, more preferably 15% by mass, still more preferably 10% by mass, and yet more preferably 8% by mass. When the content of the [ a1] phthalocyanine compound is within the above range, the properties relating to the visible light transmittance and infrared ray shielding property of the obtained optical filter become more favorable.

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

([ B ] adhesive resin)

[B] The binder resin is a component that holds [ a1] phthalocyanine compound and the like in the obtained optical filter and serves as a matrix.

In order to improve strength, sensitivity, heat resistance, and the like, [ B ] the binder resin preferably has a polymerizable group, and more preferably has a structural unit containing a polymerizable group. Examples of the polymerizable group include: an oxetane group, a (meth) acryloyl group, a vinyl group, an alkoxysilyl group, or the like, preferably an oxetane group, a (meth) acryloyl group, an alkoxysilyl group, or a combination thereof, and more preferably a (meth) acryloyl group.

Examples of the monomer providing the structural unit 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 ] meth (acrylic acid)^2.6]Decyl ester, 3-methacryloxypropyltriethoxysilane, and the like.

Further, the structural unit containing a polymerizable group can also be introduced by, for example, reacting a compound having a polymerizable group such as a group reactive with a carboxyl group (an oxetanyl group, or the like) or a (meth) acryloyl group with a resin containing a structural unit having a carboxyl group.

The lower limit of the content of the structural unit having a polymerizable group in the [ B ] binder resin is preferably 5% by mass, more preferably 10% by mass, 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 ] binder resin. On the other hand, the upper limit of the content is preferably 95% by mass, more preferably 90% by mass, and still more preferably 85% by mass.

In order to improve heat resistance, [ B ] the binder resin preferably has a ring structure in the main chain. The number of ring elements of the ring structure is, for example, 3 to 12, preferably 5 to 8.

Examples of monomers that provide structural units having a ring structure in the main chain include N-substituted maleimide monomers and cyclic olefins.

The N-substituted maleimide monomer is a compound in which a hydrogen atom bonded to a nitrogen atom in maleimide is substituted with a substituent. The substituent is preferably a hydrocarbon group, more preferably a hydrocarbon group having a ring structure, and still more preferably an aromatic hydrocarbon group. Examples of the N-substituted maleimide monomer include: n-phenylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, N-methylmaleimide and the like.

Examples of the cycloolefin include: norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, and the like.

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

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

[B] The binder resin preferably contains an acidic group. Examples of the acidic group include: carboxyl group, acid anhydride group, phenolic hydroxyl group, sulfo group, etc. Among these, carboxyl groups are also preferable as the acidic groups. [B] The binder resin is preferably a resin containing a structural unit having one or more acidic groups. In the case where [ B ] the binder resin has an acidic group, good alkali solubility can be exhibited. When the binder resin [ B ] is alkali-soluble, alkali development can be carried out, and an optical filter having a desired pattern shape can be formed.

Examples of the monomer that provides a structural unit containing an acidic group include carboxyl group-containing monomers such as: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, and anhydrides thereof; mono [ (meth) acryloyloxyalkyl ] esters of divalent or more polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl ] succinate and mono [2- (meth) acryloyloxyethyl ] phthalate; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate.

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

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

[B] The binder resin may further comprise other structural units. Examples of monomers providing other structural units include:

aromatic vinyl compounds such as styrene, alpha-methylstyrene, p-hydroxystyrene, p-hydroxy-alpha-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene,

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) acrylates such as decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane and the like,

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0^2，6]Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane, etc,

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

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

[B] The weight average molecular weight (Mw) of the binder resin in terms of polystyrene is preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and even more preferably 4,000 to 30,000, among values measured by a Gel Permeation Chromatography (GPC) method. When Mw is in the above range, the binder resin [ B ] having excellent solubility in a solvent or a developer and sufficient mechanical properties can be obtained.

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 still more preferably 20 mass%. On the other hand, the upper limit of the content is preferably 70% by mass, more preferably 60% by mass, and still more preferably 50% by mass. When the content of the binder resin [ B ] is within the above range, the properties related to the visible light transmittance and the infrared ray shielding property of the obtained optical filter can be sufficiently exhibited, and the heat resistance and the like can be improved.

([ C ] Infrared screening agent)

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

About as [ C ]]Examples of the metal oxide of the infrared shielding agent include: tungsten oxide compound and quartz (SiO)₂) Magnetite (Fe)₃O₄) Alumina (Al)₂O₃) Titanium dioxide (TiO)₂) Zirconium oxide (ZrO)₂) Spinel (MgAl)₂O₄) And the like.

Examples of the copper compound as the [ C ] infrared shielding agent include copper phthalocyanine compounds and other copper complexes. Examples of the copper phthalocyanine-based compound include copper phthalocyanine, copper chloride bromide phthalocyanine, and copper bromide phthalocyanine.

The infrared shielding agent [ C ] is preferably a metal oxide, and more preferably a tungsten oxide-based compound. The tungsten oxide-based compound is an infrared shielding agent having high absorption of infrared rays (particularly, infrared rays having a wavelength of about 800nm or more and 1200nm or less) (that is, high shielding properties against infrared rays) and low absorption of visible light. Therefore, when the composition (I) contains a tungsten oxide compound, the infrared shielding property can be improved while maintaining the good visible light transmittance of the obtained optical filter. [C] The infrared shielding agent may be used alone or in combination of two or more.

The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following formula (3).

A_xWO_y…(3)

In the formula (3), A is a metal element. X is more than or equal to 0.001 and less than or equal to 1.1. Y is more than or equal to 2.2 and less than or equal to 3.0.

As the metal element represented by a in the formula (3), there can be mentioned: 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 and the like. The metal element represented by a may be one kind or two or more kinds.

The 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.

When x in the formula (3) is 0.001 or more, infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, more preferably 0.1. On the other hand, when x is 1.1 or less, the formation of an impurity phase in the tungsten oxide-based compound can be more reliably avoided. The upper limit of x is preferably 1, more preferably 0.5.

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

Specific examples of the tungsten oxide-based compound represented by the formula (3) include Cs_0.33WO₃、Rb_0.33WO₃、K_0.33WO₃、Ba_0.33WO₃Etc., preferably Cs_0.33WO₃And Rb_0.33WO₃More preferably Cs_0.33WO₃。

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

[C] The infrared shielding agent can also be synthesized by a known method and can be obtained as a commercially available product. In the case where 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. The tungsten oxide-based compound can be obtained as a dispersion of tungsten fine particles such as "YMF-02" from sumitomo metal mining corporation, for example.

The lower limit of the content of the infrared shielding agent [ C ] in the total solid content of the composition (I) is preferably 1 mass%, more preferably 5 mass%, still more preferably 10 mass%, and yet more preferably 15 mass%. On the other hand, the upper limit of the content is preferably 70% by mass, more preferably 50% by mass, still more preferably 40% by mass, and yet more preferably 30% by mass. When the content of the infrared shielding agent [ C ] is in the above range, the properties of the obtained optical filter with respect to visible light transmittance and infrared shielding property become more favorable.

The lower limit of the mass ratio ([ C ]/[ a1]) of the content of the [ C ] infrared shielding agent to the content of the [ a1] phthalocyanine compound is preferably 1, preferably 2, and more preferably 3. On the other hand, the upper limit of the mass ratio ([ C ]/[ a1]) is preferably 40, more preferably 20, and still more preferably 10. When the content ratio of the [ a1] phthalocyanine compound to the [ C ] infrared-shielding agent is within the above range, the properties relating to the visible light transmittance and infrared-shielding property of the obtained optical filter become better.

([ D ] dispersant)

The composition (I) preferably further comprises [ D ] a dispersant. The dispersant [ D ] improves the uniform dispersibility of the infrared shielding agent [ C ] (particularly, a metal oxide), and the optical filter obtained has more excellent properties with respect to visible light transmittance and infrared shielding property.

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

[D] Examples of the dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116, BYK-LPN 22102 (manufactured by BYK), urethane dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-2164 (manufactured by BYK), sponby-lubri (r) (manufactured by spok), lubro-lubri-sol-51 (manufactured by lubro), examples of the polyester-based dispersant include agkispa (Ajisper) PB821, agkispa (Ajisper) PB822, agkispa (Ajisper) PB880, and agkispa (Ajisper) PB881 (manufactured by Ajinomoto Fine chemistry (Ajinomoto Fine-Techno) (stock Co., Ltd.) as described above), and Bike (BYK) -LPN21324 (manufactured by bike chemical (BYK) Co., Ltd.).

The lower limit of the amine value of the dispersant [ D ] is preferably 10mgKOH/g, more preferably 40mgKOH/g, and still more preferably 80 mgKOH/g. On the other hand, the upper limit of the amine value is preferably 300mgKOH/g, more preferably 200mgKOH/g, and still more preferably 160 mgKOH/g. By using the dispersant having an amine value, the dispersibility of the [ C ] infrared shielding agent is improved, and the properties of the optical filter obtained can be further improved. The "amine value" is the number of mg of KOH in equivalent to 1g of HCl required to neutralize the dispersant solid.

The lower limit of the content of the dispersant is preferably 5 parts by mass, more preferably 10 parts by mass, and still more preferably 20 parts by mass with respect to 100 parts by mass of the infrared shielding agent [ C ]. On the other hand, the upper limit of the content is preferably 200 parts by mass, more preferably 100 parts by mass, and still more preferably 60 parts by mass.

([ E ] polymerizable Compound)

The composition (I) preferably further contains [ E ] a polymerizable compound. When the composition (I) contains the polymerizable compound [ E ], it can exhibit good curability, good heat resistance of the optical filter to be obtained, and the like. The polymerizable compound [ E ] is a compound having two or more polymerizable groups. Further, the [ B ] binder resin having two or more polymerizable groups is not contained in the [ E ] polymerizable compound. Examples of the polymerizable group include an ethylenically unsaturated 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. [E] One or a mixture of two or more of the polymerizable compounds may be used.

Examples of the compound having two or more (meth) acryloyl groups include: polyfunctional (meth) acrylates such as a reactant of an aliphatic polyhydroxy compound and (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional (meth) acrylates modified with alkylene oxide, polyfunctional urethane (meth) acrylates such as a reactant of a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, polyfunctional (meth) acrylates having a carboxyl group such as a reactant of a (meth) acrylate having a hydroxyl group and an acid anhydride, and the like.

Here, as the aliphatic polyhydric compound, for example, there can be mentioned: 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) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include: toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include: a dibasic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride, or a tetrabasic acid dianhydride such as pyromellitic dianhydride, biphenyltetracarboxylic dianhydride or benzophenonetetracarboxylic dianhydride.

Specific examples of the compound having two or more (meth) acryloyl groups include: omega-carboxy polycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol fluorene di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2' -ethyleneoxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, propylene glycol di (, Dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, urethane (meth) acrylate compounds, and the like.

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

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Specific examples of the compound having two or more N-alkoxymethylamino groups include: n, N ', N ", N ″ -hexa (alkoxymethyl) melamine, N ' -tetrakis (alkoxymethyl) benzoguanamine, N ' -tetrakis (alkoxymethyl) glycoluril, and the like.

The lower limit of the content of the [ E ] polymerizable compound in the total solid content of the composition (I) is preferably 5% by mass, more preferably 10% by mass, and still more preferably 20% by mass. On the other hand, the upper limit of the content is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass.

([ F ] polymerization initiator)

The composition (I) preferably contains [ F ] a polymerization initiator. The polymerization initiator [ F ] includes a photopolymerization initiator, a thermal polymerization initiator and the like, and is preferably a photopolymerization initiator. This can impart photosensitivity (radiation sensitivity) to the composition (I). The photopolymerization initiator is a compound that generates an active species that initiates polymerization of the [ E ] polymerizable compound or the like by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. [F] The polymerization initiator may be used singly or in combination of two or more.

Examples of the [ F ] polymerization initiator include: thioxanthone compounds, acetophenone compounds, bisimidazole 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, and the like. Among these, preferred are thioxanthone-based compounds, acetophenone-based compounds, bisimidazole-based compounds, triazine-based compounds and O-acyloxime-based compounds, and more preferred are O-acyloxime-based compounds.

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

Examples of the acetophenone-based compound include: 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

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

In the case of using a bisimidazole-based compound, it is preferable to use a hydrogen donor in combination from the viewpoint that the sensitivity can be improved. The "hydrogen donor" as used herein refers to a compound which can donate a hydrogen atom to a radical generated from a biimidazole-based compound by exposure to light. Examples of the hydrogen donor include thiol hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; amine-based hydrogen donors such as 4, 4 '-bis (dimethylamino) benzophenone and 4, 4' -bis (diethylamino) benzophenone.

Examples of the triazine-based compound include those described in Japanese patent application laid-open No. 57-6096 and Japanese patent application laid-open No. 2003-238898 in paragraphs [0063] to [0065 ].

Examples of the O-acyloxime compound 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-tetrahydrofurylmethoxybenzoyl) -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-acetyl oxime), and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by Addick (ADEKA) Co., Ltd., supra), OXE-03, OXE-04 (manufactured by BASF corporation, supra), and the like can be used.

When a photopolymerization initiator is used, a sensitizer may be used in combination. Examples of the sensitizer include: 4, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like.

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

(other organic pigments)

The composition (I) may contain a known organic dye other than the [ A1] phthalocyanine compound and the copper compound as the [ B ] infrared-screening agent. Examples of the other organic coloring matter include a diimine compound, a squarylium compound, a cyanine compound, a naphthalocyanine compound, a quacrylene compound, an ammonium compound, an imine compound, an azo compound, an anthraquinone compound, a porphyrin compound, a pyrrolopyrrole compound, an oxonol compound, a ketanium compound, a six-membered porphyrin (hexaphyrin) compound, and the like (except those containing a copper atom). Further, the phthalocyanine compound [ A1] and a phthalocyanine compound other than the phthalocyanine compound [ B ] as the infrared shielding agent may be used.

Further, 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 phthalocyanine compound [ a ] is preferably 600nm, and more preferably 650 nm. On the other hand, the upper limit of the maximum absorption wavelength of the phthalocyanine compound [ a ] is preferably 900nm, more preferably 850nm, even more preferably 800nm, 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 10nm, and more preferably 30 nm. On the other hand, the upper limit of the difference is preferably 100nm, more preferably 80nm, and still more preferably 60 nm. [a] Examples of the phthalocyanine compound include various conventionally known phthalocyanine compounds.

The lower limit of the content of the [ a1] phthalocyanine compound in the total organic pigments in the composition (I) is preferably 50% by mass, more preferably 70% by mass, sometimes more preferably 80% by mass, sometimes more preferably 90% by mass, and sometimes more preferably 99% by mass. It may be preferable that the organic dye substantially contains only the [ A1] phthalocyanine compound. The composition (I) can improve productivity by reducing the content of other organic pigments in the manner described.

(additives)

The composition (I) may contain various additives as required in addition to the components [ A1] to [ F ] and other organic pigments.

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

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

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-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

As the antioxidant, there may be mentioned: 2, 2-thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butylphenol, pentaerythritol tetrakis [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, thiodivinylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like. The content of the antioxidant is usually 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [ a ] phthalocyanine compound.

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

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

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, 4-amino-1, 2-butanediol, and the like.

Examples of the developing property improving agent include: succinic acid mono [2- (meth) acryloyloxyethyl ] ester, phthalic acid mono [2- (meth) acryloyloxyethyl ] ester, omega-carboxy polycaprolactone mono (meth) acrylate, and the like.

Examples of the reaction modifier include polyfunctional thiols.

The lower limit of the content of the components other than the components [ A1] to [ F ] and the other organic pigments in the total solid content 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, and more preferably 5% by mass.

(solvent)

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

Examples of the solvent include:

(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 monoethyl 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, and mixtures thereof,

Alkyl lactate such as methyl lactate and ethyl lactate,

(cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol and cyclohexanol, etc,

Ketols 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, and the like,

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

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

Diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate and 1, 6-hexanediol diacetate,

Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl-3-methoxybutylpropionate,

Other esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl 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, and ethyl 2-oxobutyrate, and the like,

Aromatic hydrocarbons such as toluene and xylene,

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

The content of the solvent in the composition (I) is not particularly limited. The lower limit of the solid content concentration (total concentration of the components excluding the solvent) in the composition (I) is preferably 5% by mass, and more preferably 10% by mass. On the other hand, the upper limit of the solid content concentration is preferably 50% by mass, and more preferably 40% by mass. When the solid content concentration is within the above range, dispersibility, stability, coatability, and the like are further improved.

(preparation method)

The method for producing the composition (I) is not particularly limited, and the composition can be produced by mixing the respective components. For example, in the case where the composition contains a metal oxide as [ C ] infrared ray-screening agent and a dispersant as [ D ], the following method can be employed: first, a dispersion liquid containing [ C ] an infrared shielding agent, [ D ] a dispersant and a solvent is prepared, and [ A1] a phthalocyanine compound, [ B ] a binder resin and optionally other components are added to the dispersion liquid and mixed. The dispersion or the composition (I) may be subjected to a filtration treatment to remove aggregates, if necessary.

< composition for optical sensor (II) >

The composition (II) for an optical sensor (hereinafter, also simply referred to as "composition (II)") according to an embodiment of the present invention contains [ a2] phthalocyanine compound. [A2] The phthalocyanine compound is a compound represented by the following formula (2). The composition (II) contains the [ a2] phthalocyanine compound, and thus can form an optical filter having few defects such as foreign substances and having good characteristics with respect to visible light transmittance and infrared shielding properties.

[ solution 5]

In the formula (2), each of the plurality of R is independently a substituted alkyl group or a substituted aryl group. And X's are each independently a hydrogen atom, a halogen atom or an alkyl group. Multiple xs may also be bonded to each other and together with the bonded carbon chains 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 of 3 to 6.

The [ a2] phthalocyanine compound is the same as the [ a1] phthalocyanine compound except that the plurality of R are each independently a substituted alkyl group or a substituted aryl group. [A2] The preferable form of the phthalocyanine compound is also the same as the [ A1] phthalocyanine compound.

The composition (II) is the same as the composition (I) except that the [ A2] phthalocyanine compound is contained instead of the [ A1] phthalocyanine compound and the [ B ] binder resin is not an essential component. The composition (II) preferably contains [ B ] a binder resin. Otherwise, the specific form and preferred form of the composition (II) are the same as those of the composition (I).

< Infrared-ray Shielding film >

An infrared shielding film for an optical filter can be formed from the composition (I) and the composition (II) according to one embodiment of the present invention (hereinafter, the composition (I) and the composition (II) are also collectively referred to simply as "composition"). The infrared shielding film has less defects such as foreign matter and has excellent characteristics relating to visible light transmittance and infrared shielding properties.

The infrared shielding film can be formed by the following method, for example. First, the composition is applied to a support, and then prebaked to evaporate a solvent, thereby forming a coating film. Then, after the coating film is exposed, the coating film is developed with a developer, and unexposed portions of the coating film are dissolved and removed. Thereafter, the infrared shielding film (I) patterned into a predetermined shape can be obtained by post-baking. In the case where the composition does not contain the [ E ] polymerizable compound and the [ F ] polymerization initiator, the composition may be cured without exposure to light or the like. In addition, the development process may not be performed, and in this case, an unpatterned infrared shielding film may be formed.

As the support to which the composition is applied, the transparent substrate, the microlens, the color filter, and the like are suitable. The coating can be carried out by any suitable coating method such as spray coating, roll coating, spin coating (spin coating), slot die coating (slit coating), and bar coating.

The conditions for the heat drying of the prebaking are, for example, 70 ℃ to 110 ℃, 1 minute to 10 minutes inclusive.

Examples of the light source of the radiation used for the exposure of the coating film include: a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halogen lamp, a medium-pressure mercury lamp, or a low-pressure mercury lamp, or a laser light source such as an argon ion laser, a Yttrium Aluminum Garnet (YAG) laser, a XeCl excimer laser, or a nitrogen laser. As the exposure light source, an ultraviolet Light Emitting Diode (LED) may be used. The wavelength is preferably in the range of 190nm to 450 nm. The exposure amount of the radiation is usually 10J/m²Above and 50,000J/m²About the following.

The developer is usually an alkaline developer. The alkaline developer is preferably an aqueous solution of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, or the like. The alkaline developer may be added with an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant. After the development, washing with water is usually performed.

As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a spin-immersion (dip) developing method, or the like can be applied. The developing conditions are about 5 seconds to 300 seconds at normal temperature.

The conditions for the post-baking are usually 180 ℃ to 280 ℃ and 1 minute to 60 minutes.

The lower limit of the average film thickness of the infrared shielding film formed in the above manner is usually 0.5 μm, and preferably 1 μm. On the other hand, the upper limit of the average film thickness is usually 10 μm, preferably 5 μm. When the average film thickness by infrared shielding is within the above range, the balance between visible light transmittance and infrared shielding property becomes better.

< optical Filter >

An infrared shielding film formed from the composition of an embodiment of the present invention can be used in an optical filter. The optical filter having the infrared shielding film has less defects such as foreign matter and has excellent characteristics relating to visible light transmittance and infrared shielding property. The optical filter is used as an optical filter of an optical sensor such as a solid-state imaging element.

The optical filter may be an optical filter including only the infrared shielding film, or may be an optical filter including the infrared shielding film and other constituent members. For example, the optical filter may be a laminate having the infrared shielding film and another layer.

The infrared shielding film is preferably incorporated as a constituent member 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) as a single body. By incorporating the infrared shielding film in an optical sensor, a large process margin and the like can be obtained. The infrared shielding film (when incorporated in the solid-state imaging device, the infrared shielding film may be disposed on the outer surface side of the microlens of the solid-state imaging device, between the microlens and the color filter, between the color filter and the photodiode, or the like.

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

Optical sensors such as solid-state imaging devices including the optical filter are useful in digital still cameras, cameras for mobile phones, digital video cameras, Personal Computer (PC) cameras, monitoring cameras, cameras for automobiles, portable information terminals, computers, video games, medical equipment, and the like.

< optical sensor >

The optical filter is used in an optical sensor such as a solid-state imaging element. Since the optical filter has excellent characteristics relating to visible light transmittance and infrared shielding property with little defects such as foreign matter, an optical sensor such as a solid-state imaging element having the optical filter has high sensitivity, high color reproducibility, and the like, and is excellent in practical use.

Hereinafter, a solid-state imaging device will be described as an example of the 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 sequentially stacked. In addition, a planarization layer may be provided between these layers. Light is incident from the microlens side in the solid-state imaging element. Incident light passes through the microlens and the color filter to reach the photodiode. The color filters are configured such that only light in a specific wavelength range is transmitted through each of R (red), G (green), and B (blue) filters, for example.

In the solid-state imaging device, the optical filter (infrared shielding film) may be provided on an outer surface side of the microlens, between the microlens and the color filter, between the color filter and the layer in which the plurality of photodiodes are arranged, or the like. The optical filter is preferably laminated between the microlens and the color filter or between the color filter and the photodiode. Further, other layers (e.g., a planarization layer) may be further provided between the optical filter and the microlens, the color filter, the photodiode, and the like.

Specific examples of the solid-state imaging device include a CCD and a CMOS as a camera module. The solid-state imaging element is useful in a digital still camera, a camera for a mobile phone, a digital video camera, a PC camera, a monitoring camera, a camera for an automobile, a portable information terminal, a computer, a video game, a medical device, and the like.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

< Synthesis example 1> Synthesis of Phthalocyanine Compound (a-1)

32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline, 4.76g of vanadium trichloride and 13.74g of DBU were stirred in 100mL of 1-pentanol at an internal temperature of 125 ℃ for 24 hours. Then, 600mL of methanol was added, and the precipitate was filtered off and dried. Purification was carried out by column chromatography (silica gel/toluene) to obtain 11.2g 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 analysis results.

·MS：(EI)m/z 2245M+

Elemental analysis value: found (C: 68.44%, H: 6.44%, N: 4.99%);

theoretical value (C: 68.47%, H: 6.46%, N: 4.99%)

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 734.5nm and a gram absorption coefficient of 6.75X 10⁴mL/g·cm。

[ solution 6]

In the formula, "+" indicates a bond (the same applies to the following chemical formula).

< Synthesis example 2> Synthesis of Phthalocyanine Compound (a-2)

14.5g of a green powder was obtained in the same manner as in Synthesis example 1, except that 18.6g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline was used in place of 32.9g of 4, 7-bis (4-methoxybutyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The obtained compound was confirmed to be the target compound (a-2) represented by the following formula (a-2) from the following analysis results.

·MS：(EI)m/z 1267M+

Elemental analysis value: found (C: 68.20%, H: 7.66%, N: 8.82%);

theoretical value (C: 68.17%, H: 7.63%, N: 8.83%)

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 734.0nm and a gram absorption coefficient of 1.21X 10⁵mL/g·cm。

[ solution 7]

< Synthesis example 3> Synthesis of Phthalocyanine Compound (a-3)

5.9g of a green powder was obtained in the same manner as in Synthesis example 1 except that 29.4g of 4, 7-bis (4- (3-methoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline was used in place of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline 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 analysis results.

·MS：(EI)m/z 2003M+

Elemental analysis value: found (C: 71.85%, H: 6.44%, N: 5.57%);

theoretical value (C: 71.87%, H: 6.43%, N: 5.59%)

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 735.5nm and a gram absorption coefficient of 7.40X 10⁴mL/g·cm。

[ solution 8]

< Synthesis example 4> Synthesis of Phthalocyanine Compound (a-4)

11.2g of a green powder was obtained in the same manner as in Synthesis example 1, except that 28.0g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline was used in place of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The obtained compound was confirmed to be the target compound (a-4) represented by the following formula (a-4) from the following analysis results.

·MS：(EI)m/z 1908M+

Elemental analysis value: found (C: 70.49%, H: 5.51%, N: 5.85%);

theoretical value (C: 70.47%, H: 5.49%, N: 5.87%)

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 735.5nm and a gram absorption coefficient of 7.89X 10⁴mL/g·cm。

[ solution 9]

< Synthesis example 5> Synthesis of Phthalocyanine Compound (a-5)

31.0g of a green powder was obtained in the same manner as in Synthesis example 1 except for using 38.8g of 4, 7-bis (4- ((1, 6-dimethoxynaphthalen-2-yl) oxy) butyl) -1, 3-diiminobenzisoindoline in place of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The obtained compound was confirmed to be the target compound (a-5) represented by the following formula (a-5) from the following analysis results.

·MS：(EI)m/z 2645M+

Elemental analysis value: found (C: 72.62%, H: 6.05%, N: 4.30%);

theoretical value (C: 72.63%, H: 6.10%, N: 4.23%)

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 735.5nm and a gram absorption coefficient of 5.85X 10⁴mL/g·cm。

[ solution 10]

< Synthesis example 6> Synthesis of Phthalocyanine Compound (a-6)

28.1g of a green powder was obtained in the same manner as in Synthesis example 1 except that 19.4g of 4, 7-bis (4- ((1, 6-dimethoxynaphthalen-2-yl) oxy) butyl) -1, 3-diiminobenzisoindoline and 16.5g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline were used in place of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The obtained compound was confirmed to be the target compound (a-6) represented by the following formula (a-6) from the agreement of m/z of each component by a liquid chromatography mass spectrometer (LC-MS).

A toluene solution of the compound obtained in the manner described showed a maximum absorption at 735.5nm and a gram absorption coefficient of 6.30X 10⁴mL/g·cm。

[ solution 11]

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

< Synthesis example 7> Synthesis of Phthalocyanine Compound (a' -1)

According to the description of example (65) of Japanese patent laid-open publication No. Hei 02-138382, phthalocyanine (a' -1) for comparative example (maximum absorption wavelength 725nm) represented by the following formula was synthesized.

[ solution 12]

< Synthesis example 8> Synthesis of Phthalocyanine Compound (a' -2)

A phthalocyanine compound (a' -2) (maximum absorption wavelength 728nm) for comparative examples represented by the following formula was synthesized by the method described in paragraph [0075] (example 4) of Japanese patent laid-open No. 2016-204536.

[ solution 13]

< Synthesis example 9> Synthesis of Phthalocyanine Compound (a' -3)

Other phthalocyanine compounds (a' -3) (having a maximum absorption wavelength of 692nm) for pigments represented by the following formula were synthesized by the method described in paragraphs [0020] to [0025] (example 1) of Japanese patent laid-open No. H05-25177.

[ solution 14]

< Synthesis example 10> Synthesis of Cesium tungsten oxide powder

Use of paragraph [0113 ] of Japanese patent No. 4096205]Synthesis of cesium tungsten oxide (Cs) by the method described in (1)_0.33WO₃) And (3) powder.

< 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 an α -methylstyrene dimer were further charged. After the inside of the reaction vessel was purged with nitrogen, the reaction vessel was heated at 80 ℃ for 5 hours while stirring and nitrogen bubbling (nitrogenbubbling) was performed, thereby obtaining a solution containing the binder resin (B-1) (binder resin solution (B-1): solid content concentration 35 mass%). The obtained binder resin (b-1) was subjected to measurement of the molecular weight in terms of polystyrene using a Gel Permeation Chromatography (GPC) apparatus (GPC-104 type, column: 3 groups of LF-604 produced by Showa Denko K.K. and KF-602, and developing solvent: tetrahydrofuran), and as a result, the weight-average molecular weight (Mw) was 9700, the number-average molecular weight (Mn) was 5700, and the Mw/Mn was 1.70. In the present synthesis example, the input ratio (mass ratio) of each monomer and the content ratio (mass ratio) of the constitutional unit derived from each monomer in the obtained binder resin can be regarded as substantially the same (the same applies to synthesis example 14 below).

< Synthesis example 12> Synthesis of Binder resin (b-2)

Into a flask equipped with a cooling tube and a stirrer, 200 parts by mass of propylene glycol monomethyl ether was charged and the temperature was raised to 80 ℃. 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 at the same temperature over 3 hours, and polymerization was carried out while maintaining the temperature after the addition. Thereafter, the temperature of the reaction solution was raised to 100 to 120 ℃ and the reaction was further carried out for 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 charged, and the temperature was raised to 110 ℃ to carry out a reaction for 9 hours, thereby obtaining a solution containing a binder resin (B-2) represented by the following formula (binder resin solution (B-2): solid content concentration 40 mass%). The molecular weight of the obtained binder resin was measured in the same manner as in synthetic example 11, and as a result, the weight average molecular weight (Mw) was 15100, the number average molecular weight (Mn) was 7000, and the Mw/Mn was 2.16.

[ solution 15]

(in the formula, the composition ratio is a mass ratio)

< Synthesis example 13> Synthesis of Binder resin (b-3)

Into a flask equipped with a cooling tube and a stirrer, 200 parts by mass of propylene glycol monomethyl ether was charged and the temperature was raised to 80 ℃. 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 at the same temperature over 3 hours, and polymerization was carried out while maintaining the temperature after the addition. Thereafter, the temperature of the reaction solution was raised to 100 to 120 ℃ and the reaction was further carried out for 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 charged, and the temperature was raised to 110 ℃ to carry out a reaction for 30 hours, thereby obtaining a solution containing a binder resin (B-3) represented by the following formula (binder resin solution (B-3): solid content concentration 40 mass%). The obtained binder resin was measured for molecular weight in the same manner as in synthetic example 11, and as a result, the weight average molecular weight (Mw) was 17000, the number average molecular weight (Mn) was 7700, and Mw/Mn was 2.21.

[ solution 16]

(in the formula, the composition ratio is a mass ratio)

< 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 further 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 nitrogen substitution was performed, followed by slowly stirring to raise the temperature of the solution to 80 ℃. Polymerization was carried out while maintaining the temperature for 5 hours, thereby obtaining a solution containing the binder resin (B-4) (hereinafter, the binder resin solution (B-4) solid content concentration was 35 mass%). The obtained binder resin was measured for molecular weight in the same manner as in synthetic example 11, and found to have a weight average molecular weight (Mw) of 9500, a number average molecular weight (Mn) of 5800, and an Mw/Mn of 1.64.

< Synthesis example 15> dispersant (d-2)

Using a method described in literature (Macromolecules 1992, 25, p5907-5913), 45 parts by mass of dimethylaminoethyl methacrylate, 20 parts by mass of 2-ethylhexyl methacrylate, 5 parts by mass of n-butyl methacrylate, and PME-200 (methoxypolyethylene glycol monomethacrylate and CH 5907-5913) were mixed₂＝C(CH₃)COO(C₂H₄O)_n-CH₃

Polymer of the indicated monomer) 30 parts by mass were collectively polymerized to obtain a reaction solution containing a non-copolymer. Then, the reaction solution was quenched with methanol, and the resulting reaction solution was washed with a 7 mass% aqueous solution of sodium hydrogencarbonate followed by water. Thereafter, a solvent substitution with Propylene Glycol Monomethyl Ether Acetate (PGMEA) was carried out to obtain a dispersant solution (D-2) containing the dispersant (D-2) in a yield of 80% by mass. The obtained dispersant (D-2) had an amine value of 160mgKOH/g, Mw of 9500, Mw/Mn of 1.21 and a solid content of the dispersant solution (D-2) of 39.6% by mass.

Production example 1 preparation of Dispersion (C-1)

25.00 parts by mass of the above-mentioned cesium tungsten oxide, 13.30 parts by mass of "BYK (BYK) -LPN 6919" (solid content concentration: 60% by mass, amine value: 120mgKOH/g) of BYK chemical (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 charged in a container together with 2000 parts by mass of zirconia particles having a diameter of 0.1mm, and dispersed by a paint shaker, thereby obtaining a dispersion (C-1) having an average particle diameter (D50) of 19 nm. The average particle size was measured by a Dynamic Light Scattering (DLS) method using a light Scattering measuring instrument ("ALV-5000" of ALV, Germany).

Production example 2 preparation of Dispersion (C-2)

A dispersion (C-2) having an average particle diameter of 19nm 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 CPN54.80 parts by mass.

Production example 3 preparation of dye solutions (A-1) to (A-9)

In a vessel, 5.00 parts by mass of the phthalocyanine compound (a-1) and 95.00 parts by mass of CPN as a solvent were weighed and mixed by a stirrer. The obtained solution was filtered under pressure using a 0.2 μm filter made of Polytetrafluoroethylene (PTFE) under a constant pressure of 0.05MPa, to obtain a dye solution (A-1). Further, each of the pigment solutions (a-2) to (a-6) in table 1, the pigment solution (a-8) and the pigment solution (a-9) were obtained by the same method as described above except that the phthalocyanine compound (a-2) to (a-6), the phthalocyanine compound (a-8) and the phthalocyanine compound (a-9) were used as the phthalocyanine compound.

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 CPN 94.30 parts by mass as a solvent were used.

[ example 1]

20.00 parts by mass of the dispersion (C-1), 23.15 parts by mass of the pigment 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) of Japan chemical company as a polymerizable compound, "NCI-930" (an O-acyloxime compound) of Aidic corporation (ADEKA) as a polymerization initiator, "FTX-218D" (a fluorine-based surfactant) of Naios (NEOS) as a surfactant, 0.05 parts by mass of Karenz MT 1 "(a polyfunctional thiol) of Showa Denko K and electrician as a reaction regulator, and 0.31 parts by mass of Irganox 1010 (Irganox phenol-based antioxidant) of Bass (BASF) as an antioxidant, And 25.71 parts by mass of Cyclopentanone (CNP) as a solvent were mixed by a mixer. About 100mL of the mixture was subjected to pressure filtration using a 0.5 μm Polytetrafluoroethylene (PTFE) filter under a constant pressure of 0.05MPa, to thereby obtain the composition of example 1.

Examples 2 to 13 and comparative examples 1 to 3

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 total amount and blending amount (parts by mass) of the dispersion liquid, the pigment solution and the binder resin solution, and the blending amount (parts by mass) of the polymerizable compound, the polymerization initiator, the surfactant, the reaction modifier, the antioxidant and the solvent were as shown in table 1. Further, Table 1 also shows [ A ] in each of the obtained compositions]Phthalocyanine compound, [ B]Binder resin, [ C ]]Infrared shielding agent, [ D ]]The type of dispersant and other pigments, and the content of solid components. "CsWO" in Table 1 represents cesium tungsten oxide (Cs) obtained in Synthesis example 10_0.33WO₃)。

[ evaluation ]

Using each of the obtained compositions, the following evaluations were performed. The evaluation results are shown in table 1.

Each composition was applied to a glass substrate by a spin coating method so as to have a predetermined film thickness. Thereafter, the coating film was heated at 100 ℃ for 120 seconds to 500mJ/cm by an i-ray stepper²The exposure is performed in the manner of (1). Then, the glass substrate was heated at 220 ℃ for 300 seconds to form an infrared shielding film having an average thickness of 2.0 to 4.0 μm on the glass substrate. The average film thicknesses are shown in table 1. The film thickness was measured by a stylus type level difference meter ("α Step IQ" by yokuwa scientific corporation). Next, the transmittance in each wavelength region of the infrared shielding film produced on the glass substrate was measured by comparison with the glass substrate using a spectrophotometer ("V-7300" by japan spectrography). According toThe obtained spectrum was evaluated by the evaluation criteria described below.

(visible light transmittance)

The average transmittance of 430nm-580nm is calculated. When the average transmittance is less than 70%, the sensitivity decreases when the film is used as an infrared shielding film. The average transmittance was evaluated by the following criteria.

A: over 80 percent

B: more than 70 percent and less than 80 percent

C: less than 70 percent

(visible transmission window range)

The transmittance in the range of 430nm to 580nm was determined to be a range in which the transmittance was continuously 70% or more. When the continuous range of 70% or more is 175nm or more, the film is expected to have high practicability because of high sensitivity when used as an infrared shielding film. The visible transmission window range was evaluated by the following criteria.

A: over 200nm

B: 175nm or more and less than 200nm

C: less than 175nm

(Infrared ray shielding range)

The transmittance in the range of 700nm to 800nm was determined to be continuously 20% or less. When the continuous range of 20% or less is 20nm or more, it is presumed that the film has high practicability because it has a high noise shielding function when used as an infrared shielding film. The infrared ray shielding range was evaluated by the following criteria.

A: over 30nm

B: 20nm or more and less than 30nm

C: less than 20nm

(Off-Slope average)

In the range of 500nm to 750nm, the longest wavelength at which the transmittance is 80% or more is represented by (X), and the shortest wavelength at which the transmittance is 20% or less is represented by (Y), and the average Off-slope (z) is calculated by the following equation. When the average Off-Slope is 0.45 or more, it is presumed that the color reproducibility and the noise shielding function of the obtained image can be improved when the film is used as an infrared shielding film, and the practicability is high. The average Off-Slope was evaluated by the following criteria.

(Z)＝60/((Y)-(X))

AA: 0.60 or more

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

(Heat resistance)

The infrared shielding film produced on the glass substrate was heated at 260 ℃ for 300 seconds using a hot plate, and the transmittance in each wavelength region before and after heating was measured by comparison with a glass substrate using a spectrophotometer ("V-7300" by japan spectrophotometers). In this case, the absorbance of the produced infrared shielding film at the wavelength having the lowest transmittance in the range of 700nm to 800nm was (a1), the absorbance at the same wavelength after heating at 260 ℃ was (a2), and the absorbance retention was 100 × (a1)/(a2), and the heat resistance at 260 ℃ was evaluated by the following criteria. When the retention rate is 30% or more, it is presumed that when the film is used as an infrared shielding film, the film can maintain high heat resistance by being used in combination with a protective film or the like, and is highly practical. The retention rate was evaluated by the following criteria.

AA: over 90 percent

A: more than 60 percent and less than 90 percent

B: more than 30 percent and less than 60 percent

C: less than 30 percent

(Defect suppressing)

Each composition was applied onto a silicon substrate by spin coating, and the coating was cured to form a cured film having a thickness of about 1 μm. The defect density (Defect Density) of the cured film was measured using a defect/foreign matter inspection apparatus ("KLA 2351" by KLA-Tencor). It can be judged that the smaller the value of the defect density, the higher the defect suppression. The defect is a detection point having a size of 1 μm or more. Based on the defect density, the defect suppression was evaluated using the following criteria.

A：10/cm²The following

B: over 10/cm²And is 50/cm²The following

C: over 50/cm²

(Post Coating Delay (PCD) stability)

Each composition was applied to a silicon substrate by a spin coating method, and a coating film having a thickness of about 1 μm was formed in a state where the coating film was not hardened. The Defect density (Defect density) of the coating film was measured using a Defect/foreign matter inspection apparatus ("KLA 2351" by KLA-Tencor). Then, the defect density of the Coating film was measured at regular intervals, the time at which the number of defects increased by 20% or more from the initial value was measured, and the stability of the Coating film after Coating (PCD: Post Coating Delay) was evaluated by the following criteria. With respect to PCD stability, the larger the speculative value, the more practical.

A: over 24 hours

B: 12 hours or more and less than 24 hours

C: less than 12 hours

As shown in table 1, the visible light transmittance, visible light transmission window range, infrared ray shielding range, average Off-Slope, heat resistance, defect suppression, and PCD stability of examples 1 to 13 were all evaluated well. Further, it is found that in each of the examples using the phthalocyanine compound represented by the above formula (1), example 1 and example 3 to example 6 using the phthalocyanine compound (a-1, a-3 to a-6) having a substituent at R have higher heat resistance than example 2 using the phthalocyanine compound (a-2) having no substituent at R. In addition, it is also found that in the above examples using a phthalocyanine compound having a substituent at R, the visible light transmittance is also good in examples 1, 3 and 4.

Industrial applicability

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

Claims

1. A composition for an optical sensor, comprising:

a phthalocyanine compound represented by the following formula (1); and

a binder resin.

[ solution 1]

(in the formula (1), R is respectively and independently a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl, X is respectively and independently a hydrogen atom, a halogen atom or an alkyl, X can also be mutually bonded 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, and n is respectively and independently an integer of 3-6.)

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

3. The composition for an optical sensor according to claim 1 or 2, wherein the binder resin has an oxetanyl group, (meth) acryloyl group, an alkoxysilyl group, or a combination thereof.

4. The composition for an optical sensor according to any one of claims 1 to 3, wherein the binder resin has a ring structure in a main chain.

5. A composition for optical sensors, which contains a phthalocyanine compound represented by the following formula (2).

[ solution 2]

(in the formula (2), R is respectively and independently alkyl with substituent or aryl with substituent; X is respectively and independently hydrogen atom, halogen atom or alkyl; X can also be mutually bonded and form an aromatic ring together with the bonded carbon chain; M is two hydrogen atoms, divalent metal atoms or derivatives of trivalent or tetravalent metal atoms; n is respectively and independently an integer of 3-6.)

6. The composition for an optical sensor according to any one of claims 1 to 5, wherein the substituents which the alkyl group and the aryl group respectively represented by R have are groups having a hetero atom.

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

8. The composition for optical sensors according to any one of claims 1 to 7, further comprising an infrared shielding agent,

the infrared shielding agent is a metal oxide, a copper compound (excluding the phthalocyanine compound), or a combination thereof.

9. The composition for optical sensors according to claim 8, wherein the metal oxide is cesium tungsten oxide.