CN112789526B

CN112789526B - Composition for optical sensor

Info

Publication number: CN112789526B
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: 2023-05-30
Anticipated expiration: 2039-10-03
Also published as: CN112789526A; JPWO2020071486A1; CN116520638A; TWI803701B; JP2024020454A; JP7424300B2; KR20210071971A; WO2020071486A1; CN116520637A; TW202022050A

Abstract

Provided is a composition for an optical sensor, which can form an optical filter for an optical sensor having good characteristics relating to visible light transmittance and infrared shielding properties. The present invention provides a composition for an optical sensor, which comprises a phthalocyanine compound represented by the following formula (1) and a binder resin. In formula (1), each of the plurality of R's is independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Each of the plurality of X's is independently a hydrogen atom, a halogen atom or an alkyl group. Multiple X's may also be bonded to each other and form an aromatic ring together with these bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom. Each of the plurality of 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

Solid-state imaging devices as optical sensors are mounted in video cameras, digital cameras, mobile phones with camera functions, and the like. As a solid-state imaging device, a Charge-coupled device (Charge-CoupledDevice, CCD) image sensor, a complementary metal oxide semiconductor (Complementary metal oxide semiconductor, CMOS) image sensor, or the like is known. The sensitivity of the photodiodes provided in these solid-state imaging devices ranges from the visible light region to the infrared region. Therefore, the solid-state imaging device is provided with a filter for blocking infrared rays. The sensitivity of the solid-state imaging device can be corrected so as to approach the visual sensitivity of a human being by the optical filter (infrared ray blocking filter). In the optical sensor other than the solid-state imaging element, a filter for blocking infrared rays may be similarly provided.

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

Prior art literature

Patent literature

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

Disclosure of Invention

Problems to be solved by the invention

However, in the conventional optical filter using the phthalocyanine compound, defects such as foreign matter may occur due to the influence of compatibility or 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 pigment such as a phthalocyanine compound, if the time period after application is long, the obtained infrared shielding film is likely to have defects such as foreign matter. In the production step, it is desired to obtain an infrared shielding film having few defects such as foreign matter even if the film is cured after being left for a while after coating.

Further, the conventional optical filter is not sufficiently satisfactory in terms of visible light transmittance and infrared shielding property. Specifically, when an optical filter is used as an infrared blocking filter of an optical sensor such as a solid-state imaging device, not only a wavelength region having high visible light transmittance and low infrared transmittance but also a wavelength region having low infrared transmittance and a wavelength region having high visible light transmittance are required to be close to each other. When the optical filter having the above characteristics is used for an optical sensor such as a solid-state imaging device, sensitivity, 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 an optical filter for an optical sensor, which is capable of forming a composition for an optical sensor having few defects such as foreign matter and having excellent characteristics concerning visible light transmittance and infrared shielding property.

Technical means for solving the problems

The present invention, which has been completed to solve the above-mentioned problems, is a composition for an optical sensor, which contains a phthalocyanine compound represented by the following formula (1) and a binder resin.

[ chemical 1]

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

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

[ chemical 2]

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an optical filter for an optical sensor having few defects such as foreign matter and having excellent characteristics concerning visible light transmittance and infrared shielding properties can be provided.

Detailed Description

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

< composition for optical sensor (I) >)

The optical sensor composition (I) according to one embodiment of the present invention (hereinafter, also referred to simply as "composition (I)") contains a [ A1] phthalocyanine compound and a [ B ] binder resin. The composition preferably further contains a [ C ] infrared shielding agent which is a metal oxide, a copper compound (excluding a [ 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 has high shielding in the near infrared region (for example, a wavelength region of 700nm to 800 nm). In addition, the [ A1] phthalocyanine compound has excellent compatibility with other components. Since the composition (I) contains the [ A1] phthalocyanine compound, an optical filter having few defects such as foreign matter and having excellent characteristics concerning visible light transmittance and infrared shielding properties can be formed.

[ chemical 3]

In formula (1), each of the plurality of R's is independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Each of the plurality of X's is independently a hydrogen atom, a halogen atom or an alkyl group. Multiple X's may also be bonded to each other and form an aromatic ring together with these bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom. Each of the plurality of n is independently an integer of 3 to 6.

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

Examples of the aryl group represented by R include a monovalent group comprising 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 and a naphthyl group, and further 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 obtained optical filter.

The alkyl group and the aryl group each of which is represented by the plurality of R may have a substituent or may not have a substituent, but are preferably substituted. That is, each of the plurality of R is preferably an alkyl group having a substituent or an aryl group having a substituent. In this way, the compatibility of the [ A1] phthalocyanine compound is further improved by the plurality of R substituents, and defects such as foreign matter in the obtained optical filter are further suppressed, and the characteristics relating to the visible light transmittance and the infrared shielding property are further improved. Further, the plurality of R groups have substituents, so that the heat resistance of the obtained optical filter is also improved.

The substituent that the alkyl group and the aryl group each of the plurality of R may have may be a hydrocarbon group such as an alkenyl group or an alkynyl group, but is preferably a group having a heteroatom. The hetero atom means an atom other than a hydrogen atom and a carbon atom. The alkyl group and the aryl group each represented by the plurality of R have a substituent having a heteroatom, whereby compatibility and the like are further improved, defects such as foreign matter and the like of 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 heteroatom, 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.

Examples of the substituent having a heteroatom include: halogen atom, alkoxy group, alkylthio group, cyano group, nitro group, carboxyl group, hydroxyl group, thiol group, amino group, and the like.

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

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

Examples of alkylthio include methylthio (CH ₃ -S-), ethylthio (C) ₂ H ₅ -S-), propylthio (C) ₃ H ₇ -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. In addition, halogen atoms, methoxy groups, ethoxy groups, methylthio groups, ethylthio groups, or combinations thereof are also preferred.

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 atoms exemplified as halogen atoms of the substituent.

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

The plurality of X's may also be bonded to each other. Typically, in a plurality of X, two X's bonded to the same benzene ring are bonded to each other and form an aromatic ring together with these bonded carbon chains. Examples of the aromatic ring 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 above X is preferably a hydrogen atom. The plural X's may be the same or different, but are preferably 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 which can be a divalent cation.

Here, the derivative of a metal atom means a group of atoms including a metal atom. The trivalent metal atom means a metal atom which can become a trivalent cation. Examples of the trivalent metal atom include Al and In. The tetravalent metal atom means a metal atom which can become a tetravalent cation. Examples of the tetravalent metal atom include Si, ge, sn, and the like. Furthermore, the metal atoms also include semimetal atoms. As the derivative of the trivalent or tetravalent metal atom represented by M, there may be mentioned: alCl, alBr, alI, alOH, inCl, inBr, inI, inOH, siCl ₂ 、SiBr ₂ 、SiI ₂ 、Si(OH) ₂ 、GeCl ₂ 、GeBr ₂ 、GeI ₂ 、SnCl ₂ 、SnBr ₂ 、SnI ₂ 、Sn(OH) ₂ VO, tiO, etc.

As said M, H is preferable ₂ (two hydrogen atoms), pd, cu, zn, pt, ni, co, fe, mn, sn, in, snCl ₂ AlCl, VO and TiO, more preferably VO.

The lower limit of n is preferably 4. The upper limit of n is preferably 5, 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 further preferably 720nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000nm, more preferably 900nm, further preferably 800nm, further preferably 750nm. When the maximum absorption wavelength of the [ A1] phthalocyanine compound is within the above range, an optical filter having more favorable 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 a known method 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.

[ chemical 4]

In the formulae (i) and (ii), R, X and n have the same meaning as 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. Of 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℃and 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 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, and diethylethanol, high boiling point solvents such as dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, 1, 3-dimethyl-2-imidazolidinone (1, 3-Dimethyl imidazolidinone, DMI), and urea.

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 an alkaline organic catalyst such as 1,8-Diazabicyclo [5.4.0] -undec-7-ene (DBU) or 1,5-Diazabicyclo [4.3.0] non-5-ene (1, 5-Diazabicyclo [4.3.0] non-5-ene, DBN) may be used.

In the case where M in the formula (1) is a phthalocyanine compound having two hydrogen atoms, the phthalocyanine compound represented in the formula (i) or the 1, 3-diiminoisoindoline compound represented in the formula (ii) is reacted with sodium or potassium metal under the above-mentioned reaction conditions, and then the sodium or potassium metal as a central metal is subjected to a separation treatment with hydrochloric acid, sulfuric acid or the like.

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

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 method described in Japanese patent application laid-open No. 2003-516421 can be used for the synthesis.

The lower limit of the content of the [ A1] phthalocyanine compound in all solid components (all components except the solvent) in the composition (I) is preferably 0.1 mass%, more preferably 0.5 mass%, further preferably 1 mass%, further more preferably 2 mass%. On the other hand, the upper limit of the content is preferably 30 mass%, more preferably 15 mass%, further preferably 10 mass%, further more preferably 8 mass%. When the content of the [ A1] phthalocyanine compound is within the above range, the characteristics relating to the visible light transmittance and the infrared shielding property of the obtained optical filter become more excellent.

[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 serves as a matrix by retaining the [ A1] phthalocyanine compound or the like in the obtained optical filter.

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

Examples of the monomer that provides the structural unit containing the 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 ester, 3-methacryloxypropyl triethoxysilane, and the like.

Further, for example, a compound having a polymerizable group such as a group (for example, an oxetanyl group or an oxetanyl group) which reacts with a carboxyl group, and a (meth) acryloyl group, is reacted with a resin having a structural unit having a carboxyl group, whereby a structural unit having a polymerizable group can be introduced.

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, still more preferably 15% by mass, and still 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 mass%, more preferably 90 mass%, and further preferably 85 mass%.

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

Examples of the monomer having a structural unit having a ring structure in the main chain include N-substituted maleimide monomers, cycloolefins, and the like.

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 cycloolefins 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 may be used.

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

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

Examples of monomers that provide the structural unit containing an acidic group include monomers containing a carboxyl group: unsaturated monocarboxylic acids such as (meth) acrylic acid, butenoic acid, α -chloroacrylic acid, cinnamic acid and the like; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, or 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 -carboxyl polycaprolactone mono (meth) acrylates.

Examples of monomers having phenolic hydroxyl groups 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, more preferably 5 to 30% by mass, relative to 100% by mass of the [ B ] binder resin.

[B] The binder resin may further comprise other structural units. Examples of monomers that provide 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 (polymerization degree 2-10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2-10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2-10)10 Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ] ^2，6 ](meth) acrylic acid esters such as decane-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,

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- (ethyleneoxymethyl) -3-ethyloxetane, and the like,

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

[B] The binder resin can be obtained by polymerizing the monomers and the like by a known method. In addition, the [ B ] binder resin may be used singly or in combination of two or more.

[B] The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin is preferably 2,000 ～ 500,000, more preferably 3,000 ～ 100,000, and even more preferably 4,000 to 30,000, of the values measured by gel permeation chromatography (gel permeation chromatography, GPC). When Mw falls within the above range, the [ B ] binder resin 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 in 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 mass%, more preferably 60 mass%, and still more preferably 50 mass%. When the content of the binder resin [ B ] is within the above-mentioned range, the properties of the obtained optical filter, such as visible light transmittance and infrared shielding property, can be sufficiently exhibited, and 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 the [ A1] phthalocyanine compound), or a combination of these. As the [ C ] infrared shielding agent, a compound having a maximum absorption wavelength in a range of 800nm to 2000nm is preferable. By combining the [ C ] infrared shielding agent with the [ A1] phthalocyanine compound, the infrared shielding performance of the obtained optical filter is further improved.

Regarding [ C ]]Examples of the metal oxide of the infrared shielding agent include: tungsten oxide compound, quartz (SiO) ₂ ) Magnetite (Fe) ₃ O ₄ ) Alumina (Al) ₂ O ₃ ) Titanium dioxide (TiO) ₂ ) Zirconium oxide (ZrO) ₂ ) Spinel (MgAl) ₂ O ₄ ) Etc.

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

The infrared shielding agent [ C ] is preferably a metal oxide, more preferably a tungsten oxide compound. The tungsten oxide compound is an infrared shielding agent having high infrared (particularly, infrared having a wavelength of about 800nm to 1200 nm), high shielding property against infrared, and low absorption against visible light. Therefore, by containing the tungsten oxide compound in the composition (I), the infrared shielding property can be improved while maintaining the excellent 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 represented by the following formula (3).

A _x WO _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.

The metal element represented by a in the formula (3) may be: 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 or two or more.

The A is preferably an alkali metal, more preferably Rb and Cs, and still 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 compound can be more surely avoided. The upper limit of x is preferably 1, more preferably 0.5.

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

As specific examples of the tungsten oxide compound represented by the above formula (3), cs can be cited _0.33 WO ₃ 、Rb _0.33 WO ₃ 、K _0.33 WO ₃ 、Ba _0.33 WO ₃ Etc., preferably Cs _0.33 WO ₃ Rb _0.33 WO ₃ Further preferred is Cs _0.33 WO ₃ 。

[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, further preferably 50nm, further more preferably 30nm. When the average particle diameter is not more than the upper limit, the visible light transmittance can be further improved. On the other hand, the average particle diameter of the [ C ] infrared shielding agent is usually 1nm or more, or may be 10nm or more, for reasons such as ease of handling during production.

[C] The infrared shielding agent may be synthesized by a known method and obtained as a commercially available product. In the case where the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide 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 compound may be obtained as a dispersion of tungsten fine particles such as "YMF-02" of Sumitomo metal mine company.

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%, still more preferably 10 mass%, still more preferably 15 mass%. On the other hand, the upper limit of the content is preferably 70 mass%, more preferably 50 mass%, further preferably 40 mass%, further preferably 30 mass%. When the content of the [ C ] infrared shielding agent is within the above range, the characteristics relating to the visible light transmittance and the infrared shielding property of the obtained optical filter become more excellent.

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, more preferably 2, and further preferably 3. On the other hand, the upper limit of the mass ratio ([ C ]/[ A1 ]) is preferably 40, more preferably 20, and further preferably 10. When the content ratio of the [ A1] phthalocyanine compound to the [ C ] infrared shielding agent is within the above range, the characteristics relating to the visible light transmittance and the infrared shielding property of the obtained optical filter are improved.

([ D ] dispersant)

The composition (I) preferably further comprises a [ D ] dispersant. The [ D ] dispersant can improve the uniform dispersibility of the [ C ] infrared shielding agent (particularly, metal oxide), and the properties of the obtained optical filter concerning the visible light transmittance and infrared shielding property are improved.

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

[D] Examples of the commercially available (meth) acrylic dispersants include Disppa-Pick (Disperbyk) -2000, disppa-Pick (Disperbyk) -2001, disppa-Pick (BYK) -LPN6919, disppa-Pick (BYK) -LPN21116, and Pick (BYK) -LPN22102 (manufactured by BYK) corporation), examples of the urethane dispersants include Disppa-Pick (Disperbyk) -161, disppa-Pick (Disperbyk) -162, disppa-Pick (Disperbyk) -165, disppa-Pick (Disperbyk) -167, disppa-Pick (Disperbyk) -170, disppa-Pick) -182, disppa-Kek (Disperbyk) -2164 (manufactured by PB) corporation), solpa-Pick 76500 (Lu Borun (Lubrzi) and Focus-Pick (Founda) and further comprises, for example, disppa-Pick (Focus) 35, and Focus-Abbe (Focus) of the like, and further comprises, for example, focus-Abex (Focus-Kappab) and Focus-Kappab (Focus) carpet) 35 (Focus) and Focus-Kappab (Focus) carpet (Buppab) 35 (BYK) and Foppab (BYK) carpet (BYk) and carpet (BYk) 35.

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

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

([ E ] polymerizable Compound)

The composition (I) preferably further comprises [ E ] a polymerizable compound. When the composition (I) contains the [ E ] polymerizable compound, good curability, good heat resistance of the obtained optical filter, and the like can be exhibited. The "E" polymerizable compound means 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 or a compound having two or more N-alkoxymethylamino groups, more preferably a compound having two or more (meth) acryloyl groups. [E] The polymerizable compound may be used singly or in combination of two or more.

Examples of the compound having two or more (meth) acryloyl groups include: polyfunctional (meth) acrylates such as reactants of aliphatic polyhydroxy compounds and (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional (meth) acrylates modified with alkylene oxide, polyfunctional urethane (meth) acrylates such as reactants of (meth) acrylates having hydroxyl groups and polyfunctional isocyanates, polyfunctional (meth) acrylates having carboxyl groups such as reactants of (meth) acrylates having hydroxyl groups and anhydrides, and the like.

Here, examples of the aliphatic polyhydroxy compound include: divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, or trivalent or more 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: dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, etc., or tetrabasic acid dianhydrides such as pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, etc.

Specific examples of the compound having two or more (meth) acryloyl groups include: omega-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, diphenoxyglycolfluorene di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl methacrylate, 2- (2' -ethyleneoxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloxyethyl) 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, a polyfunctional (meth) acrylate is preferable, and a polyfunctional (meth) acrylate having 3 or more and 10 or less (meth) acryloyl groups is more preferable. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.

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

The lower limit of the content of the polymerizable compound [ E ] 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 mass%, more preferably 50 mass%, and still more preferably 40 mass%.

([ F ] polymerization initiator)

The composition (I) preferably contains [ F ] a polymerization initiator. As the [ F ] polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, etc., are exemplified, and a photopolymerization initiator is preferable. Thus, photosensitivity (radioactivity) can be imparted 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 rays, far ultraviolet rays, electron beams, X rays, or the like. [F] The polymerization initiator may be used singly or in combination of two or more.

Examples of the polymerization initiator [ F ] include: thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, alpha-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. Among these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime compounds are preferable, and O-acyl oxime compounds are more preferable.

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

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

In the case of using a bisimidazole compound, a hydrogen donor is preferably used in combination in order to improve sensitivity. The "hydrogen donor" as used herein refers to a compound that can supply a hydrogen atom to a radical generated from a bisimidazole 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 compound include compounds described in paragraphs [0063] to [0065] of Japanese patent publication No. 57-6096 and Japanese patent publication No. 2003-238898.

Examples of the O-acyloxime compound include: 1, 2-octanedione-1- [ 4- (phenylsulfanyl) phenyl ] -2- (O-benzoyl oxime), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxacyclopentyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyl oxime), and the like. As commercial products of the O-acyl oxime compound, NCI-831, NCI-930 (manufactured by ADEKA Co., ltd.), OXE-03, OXE-04 (manufactured by Basf Co., ltd.), and the like can be used.

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

(other organic pigments)

The composition (I) may contain a known organic dye other than the organic dye of the copper compound which is the [ B ] infrared shielding agent, as well as the [ A1] phthalocyanine compound. Examples of the other organic coloring matter include diimine compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quartilene compounds, ammonium compounds, imine compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, ketone onium compounds, hexaporphyrin (hexaphyrin) compounds, and the like (excluding those containing copper atoms). Further, a phthalocyanine compound other than the phthalocyanine compound used as the infrared shielding agent of [ A1] may be used.

Further, it is preferable to use a combination of the [ A1] phthalocyanine compound and 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 600nm, more preferably 650nm. On the other hand, the upper limit of the maximum absorption wavelength of the [ a ] phthalocyanine compound is preferably 900nm, more preferably 850nm, even more preferably 800nm, even more preferably 750nm. 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, more preferably 30nm. On the other hand, the upper limit of the difference is preferably 100nm, more preferably 80nm, and still more preferably 60nm. [a] The phthalocyanine compound includes 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 mass%, more preferably 70 mass%, even more preferably 80 mass%, even more preferably 90 mass%, and even more preferably 99 mass%. The organic coloring matter may preferably contain substantially only the [ A1] phthalocyanine compound. The composition (I) can improve productivity by reducing the content of other organic pigments in the manner described.

(additive)

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

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

As the surfactant, a fluorine surfactant, a silicone surfactant, and the like can be cited.

Examples of the adhesion promoter include: vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane and the like.

As the antioxidant, there may be mentioned: 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, thiodiethylebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], and the like. The content of the antioxidant may be usually 0.01 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the [ a ] phthalocyanine compound.

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

Examples of the anti-caking agent include sodium polyacrylate.

As the residue improver, there may be mentioned: 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.

As the developability improving agent, there may be mentioned: succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester, phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester, ω -carboxypolycaprolactone mono (meth) acrylate, and the like.

Examples of the reaction modifier include polyfunctional mercaptans and the like.

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

(solvent)

The composition (I) is usually prepared as a liquid composition containing a solvent (dispersion medium). As the solvent, a solvent having a proper volatility and having a proper volatility, which is obtained by dispersing or dissolving other components, is used.

Examples of the solvent include:

ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like (poly) alkylene glycol monoalkyl ethers,

Alkyl lactate such as methyl lactate and ethyl lactate,

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

Ketoalcohols such as diacetone alcohol,

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like (poly) alkylene glycol monoalkyl ether acetates,

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

Ketones such as chain ketones, e.g., methyl ethyl ketone, 2-heptanone, 3-heptanone, and cyclic ketones, e.g., cyclopentanone, cyclohexanone,

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,

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 2-oxobutyrate and other esters,

Aromatic hydrocarbons such as toluene and xylene,

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

The content of the solvent in the composition (I) is not particularly limited. The lower limit of the concentration of the solid components (the total concentration of the components 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 within the above range, dispersibility, stability, coatability, and the like become more excellent.

(preparation method)

The method for producing the composition (I) is not particularly limited, and the composition (I) can be produced by mixing the components. For example, in the case where the composition contains a metal oxide as [ C ] infrared shielding agent, and [ D ] dispersing agent, the following method can be adopted: first, a dispersion liquid containing [ C ] an infrared shielding agent, [ D ] a dispersant and a solvent is prepared, and a [ A1] 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 optionally subjected to a filtration treatment to remove aggregates.

< composition for optical sensor (II) >)

The optical sensor composition (II) according to an embodiment of the present invention (hereinafter, also simply referred to as "composition (II)") contains an [ A2] phthalocyanine compound. [A2] The phthalocyanine compound is a compound represented by the following formula (2). Since the composition (II) contains the [ A2] phthalocyanine compound, an optical filter having few defects such as foreign matter and having excellent characteristics concerning visible light transmittance and infrared shielding property can be formed.

[ chemical 5]

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

The [ A2] phthalocyanine compound is the same as the [ A1] phthalocyanine compound except that each of the plurality of R's is independently a substituted alkyl group or a substituted aryl group. [A2] The preferred 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 a [ B ] binder resin. Except for this, the specific form and preferable form of the composition (II) are the same as those of the composition (I).

< Infrared shielding film >

An infrared shielding film for an optical filter may be formed from the composition (I) and the composition (II) according to an 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 few defects such as foreign matter and has good characteristics related to visible light transmittance and infrared shielding property.

The infrared shielding film can be formed, for example, by the following method. First, the composition is applied to a support, and then prebaked to evaporate the solvent, thereby forming a coating film. Then, after exposing the coating film, development is performed using a developer, and the unexposed portions of the coating film are dissolved and removed. Thereafter, post baking is performed to obtain an infrared shielding film (I) patterned into a predetermined shape. In the case where the composition does not contain the [ E ] polymerizable compound and the [ F ] polymerization initiator, the hardening treatment such as exposure may not be performed. In this case, an unpatterned infrared shielding film may be formed.

The transparent substrate, microlens, color filter, and the like are suitable as the support to which the composition is applied. The coating may be performed by a suitable coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method (slit coating method), or a bar coating method.

The conditions for the heat drying in the pre-baking are, for example, 70 to 110 ℃ inclusive, 1 to 10 minutes inclusive.

Examples of the light source of the radiation used for exposing the coating film include: a 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, a laser light source such as an argon ion laser, an yttrium aluminum garnet (yttrium aluminum garnet, YAG) laser, a XeCl excimer laser, or a nitrogen laser, and the like. As the exposure light source, an ultraviolet light emitting diode (light emitting diode, LED) may be used. The wavelength is preferably radiation in the range of 190nm to 450 nm. The exposure to radiation is usually 10J/m ² Above and 50,000J/m ² The following is left and right.

As the developer, an alkaline developer is generally used. The alkali developer is preferably, for example, an aqueous solution of sodium carbonate, sodium hydrogencarbonate, 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. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer. Further, after development, washing with water is usually performed.

As the development treatment method, a spray development method, a dip (dip) development method, a spin-on immersion (liquid) development method, or the like can be applied. The developing condition is about 5 seconds to 300 seconds at normal temperature.

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

The lower limit of the average film thickness of the infrared shielding film formed in this manner is usually 0.5. Mu.m, preferably 1. Mu.m. On the other hand, the upper limit of the average film thickness is usually 10. Mu.m, preferably 5. Mu.m. When the average film thickness of the infrared shielding film is within the above range, the balance between the visible light transmittance and the 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 few defects such as foreign matter and has good 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 into an optical sensor such as a solid-state imaging element. In this case, the infrared shielding film functions as an optical filter (infrared cut filter) in the form of a single body. The incorporation of the infrared shielding film into the optical sensor is preferable because a large process margin can be obtained. In the case where the infrared shielding film is incorporated into the solid-state imaging device, the infrared shielding film may be disposed, for example, 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 infrared shielding film is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

The optical filter may be one in which the infrared shielding film is laminated on the 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, polyimide, and the like. The optical filter may be preferably used as an infrared cut filter or the like in a solid-state imaging device.

The optical sensor including the solid-state imaging element and the like having the optical filter is useful for digital still cameras, mobile phone cameras, digital video cameras, personal computer (Personal Computer, PC) cameras, monitoring cameras, automobile cameras, portable information terminals, computers, game machines, medical equipment, and the like.

< optical sensor >

The optical filter is used in an optical sensor such as a solid-state imaging element. The optical filter has few defects such as foreign matter and has good characteristics related to visible light transmittance and infrared shielding property, so the optical sensor such as the solid-state imaging element having the optical filter has high sensitivity, color reproducibility and the like and excellent practicality.

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

In the solid-state imaging device, the optical filter (infrared shielding film) may be provided on the outer surface side of the microlens, between the microlens and the color filter, between the color filter and the layer on 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 (planarizing layers and the like) 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 or CMOS as a camera module. The solid-state imaging device is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, portable information terminals, computers, game machines, medical equipment, and the like.

Examples

The present invention will be specifically described below based on 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 are 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 by column chromatography (silica gel/toluene) gave 11.2g of green powder. The compound obtained was confirmed to be the compound (a-1) represented by the following formula (a-1) as the target based on the analysis results described below.

·MS：(EI)m/z 2245M ⁺

Elemental analysis values: found (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 obtained in this way shows a maximum absorption at 734.5nm and a gram absorption coefficient of 6.75X10 ⁴ mL/g·cm。

[ chemical 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 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 instead of 32.9g of 4, 7-bis (4-methoxybutyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The compound obtained was confirmed to be the compound (a-2) represented by the following formula (a-2) as the target based on the analysis results described below.

·MS：(EI)m/z 1267M ⁺

Elemental analysis values: found (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 obtained in this way shows a maximum absorption at 734.0nm and a gram absorption coefficient of 1.21×10 ⁵ mL/g·cm。

[ chemical 7]

< Synthesis example 3> Synthesis of phthalocyanine compound (a-3)

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

·MS：(EI)m/z 2003M ⁺

Elemental analysis values: found (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 obtained in this way shows a maximum absorption at 735.5nm and a gram absorption coefficient of 7.40×10 ⁴ mL/g·cm。

[ chemical 8]

< Synthesis example 4> Synthesis of phthalocyanine compound (a-4)

11.2g of 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 instead of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. The compound obtained was confirmed to be the compound (a-4) represented by the following formula (a-4) as the target based on the analysis results described below.

·MS：(EI)m/z 1908M ⁺

Elemental analysis values: found (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 obtained in this way shows a maximum absorption at 735.5nm and a gram absorption coefficient of 7.89×10 ⁴ mL/g·cm。

[ chemical 9]

Synthesis example 5 Synthesis of phthalocyanine Compound (a-5)

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

·MS：(EI)m/z 2645M ⁺

Elemental analysis values: found (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 obtained in this way shows a maximum absorption at 735.5nm and a gram absorption coefficient of 5.85×10 ⁴ mL/g·cm。

[ chemical 10]

< Synthesis example 6> Synthesis of phthalocyanine compound (a-6)

28.1g of 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 instead of 32.9g of 4, 7-bis (4- (2, 6-dimethoxyphenoxy) butyl) -1, 3-diiminobenzisoindoline in Synthesis example 1. Based on the m/z matching of the respective components, the obtained compound was confirmed to be the target compound (a-6) represented by the following formula (a-6) by a liquid chromatograph/mass spectrometer (1iquid chromatography mass spectrometry,LC-MS).

The toluene solution of the compound obtained in this way shows a maximum absorption at 735.5nm and a gram absorption coefficient of 6.30X10 ⁴ mL/g·cm。

[ chemical 11]

Further, the phthalocyanine compounds (a-1) to (a-6) are each the phthalocyanine compound 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 No. Hei 02-138382, a phthalocyanine compound (a' -1) (maximum absorption wavelength 725 nm) for comparative example represented by the following formula was synthesized.

[ chemical 12]

Synthesis example 8 Synthesis of phthalocyanine Compound (a' -2)

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

[ chemical 13]

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

The phthalocyanine compound (a' -3) for other pigments represented by the following formula (the maximum absorption wavelength 692 nm) was synthesized by the method described in paragraphs [0020] to [0025] (example 1) of Japanese patent application laid-open No. 05-25177).

[ chemical 14]

< Synthesis example 10> Synthesis of cesium tungsten oxide powder

Paragraph [0113 ] using Japanese patent No. 4096205]The method described in (a) synthesizing cesium tungsten oxide (Cs _0.33 WO ₃ ) 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' -azobisisobutyronitrile and 5 parts by mass of an α -methylstyrene dimer were charged. After the inside of the reaction vessel was purged with nitrogen gas, the mixture was stirred and heated at 80℃for 5 hours while bubbling with nitrogen gas, to obtain a solution containing the binder resin (B-1) (binder resin solution (B-1): solid content concentration: 35 mass%). As the obtained binder resin (b-1), a Gel Permeation Chromatography (GPC) apparatus (GPC-104 type, column: prepared by combining 3 LF-604 and KF-602 manufactured by Showa electric company, developing solvent: tetrahydrofuran) was used, and the molecular weight in terms of polystyrene was measured, so that the weight average molecular weight (Mw) was 9700, the number average molecular weight (Mn) was 5700, and the Mw/Mn was 1.70. In this synthesis example, the ratio of the input of each unit (mass ratio) and the ratio of the content of the structural unit derived from each unit (mass ratio) 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)

200 parts by mass of propylene glycol monomethyl ether was charged into a flask equipped with a cooling tube and a stirrer, 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' -azobisisobutyronitrile was added dropwise at the same temperature over 3 hours, and polymerization was carried out for 3 hours while maintaining the temperature after the dropwise 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 catalyst amount of dimethylbenzylamine were charged, and the temperature was raised to 110℃and a reaction was carried out for 9 hours, whereby a solution (binder resin solution (B-2): solid content concentration 40% by mass) containing a binder resin (B-2) represented by the following formula was obtained. As a result of measuring the molecular weight of the obtained binder resin in the same manner as in Synthesis example 11, the weight average molecular weight (Mw) was 15100, the number average molecular weight (Mn) was 7000, and the Mw/Mn was 2.16.

[ 15]

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

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

200 parts by mass of propylene glycol monomethyl ether was charged into a flask equipped with a cooling tube and a stirrer, 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' -azobisisobutyronitrile was added dropwise at the same temperature over 3 hours, and the temperature was maintained after the addition and polymerization was carried out for 3 hours. 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 catalyst amount of dimethylbenzylamine were charged, and the temperature was raised to 110℃and a reaction was carried out for 30 hours, whereby a solution (binder resin solution (B-3): solid content concentration 40% by mass) containing a binder resin (B-3) represented by the following formula was obtained. The molecular weight of the obtained binder resin was measured in the same manner as in Synthesis example 11, and as a result, the weight average molecular weight (Mw) was 17000, the number average molecular weight (Mn) was 7700, and the Mw/Mn was 2.21.

[ 16]

/>

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

Synthesis example 14 Synthesis of Binder resin (b-4)

Into 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-methacryloxypropyl triethoxysilane, 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, followed by nitrogen substitution, and then by slow stirring and raising the temperature of the solution to 80 ℃. The polymerization was carried out at the above temperature for 5 hours, whereby a solution containing the binder resin (B-4) (hereinafter, the binder resin solution (B-4) had a solid content concentration of 35 mass%) was obtained. The molecular weight of the obtained binder resin was measured in the same manner as in Synthesis example 11, and as a result, the weight average molecular weight (Mw) was 9500, the number average molecular weight (Mn) was 5800, and the Mw/Mn was 1.64.

< Synthesis example 15> dispersant (d-2)

Dimethylaminoethyl methacrylate 45 parts by mass, 2-ethylhexyl methacrylate 20 parts by mass, and methyl methacrylate were prepared by the method described in literature (Macromolecules) 1992, 25, p 5907-5913) 5 parts by mass of n-butyl methacrylate, PME-200 (methoxypolyethylene glycol monomethacrylate and CH ₂ ＝C(CH ₃ )COO(C ₂ H ₄ O) _n -CH ₃

The polymer of the indicated monomer) 30 parts by mass were polymerized together to obtain a reaction solution containing a non-return copolymer. Then, the reaction solution was quenched with methanol, and the obtained reaction solution was washed with 7 mass% aqueous sodium bicarbonate solution and then water. Thereafter, by performing solvent substitution to propylene glycol monomethyl ether acetate (Propylene Glycol Monomethyl Ether Acetate, PGMEA), a dispersant solution (D-2) containing the dispersant (D-2) was obtained in a yield of 80 mass%. The resulting dispersant (D-2) had an amine value of 160mgKOH/g, mw of 9500, mw/Mn of 1.21 and a solid content of 39.6% by mass.

Preparation example 1 preparation of Dispersion (C-1)

25.00 parts by mass of cesium tungsten oxide, 13.30 parts by mass of "Pick (BYK) -LPN6919" (solid content concentration 60% by mass, amine value 120 mgKOH/g) of Pick chemical (BYK-Chemie) Co., as a dispersant (d-1), and 61.70 parts by mass of Cyclopentanone (CPN) as a solvent (dispersion medium) were prepared. These were filled 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 diameter was measured by a dynamic light scattering (dynamic light Scattering, DLS) method using a light scattering measuring device (ALV-5000 of ALV Corp. Germany).

Preparation 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 amount of the dispersant solution (D-2) was changed to 20.20 parts by mass and the solvent was changed to CPN54.80 parts by mass.

PREPARATION EXAMPLE 3 preparation of pigment 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. A pigment solution (A-1) was obtained by pressure filtration of the obtained solution under a constant pressure of 0.05MPa using a 0.2 μm Polytetrafluoroethylene (PTFE) filter. The respective pigment solutions (A-2) to (A-6), the pigment solution (A-8) and the pigment solution (A-9) described in Table 1 were obtained by the same method as described above, except that the phthalocyanine compounds (a-2) to (a-6), the phthalocyanine compound (a-8) and the phthalocyanine compound (a-9) were used as the phthalocyanine compounds, respectively.

The pigment 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 a solvent were used.

Example 1

In a container, 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 Japanese chemical company as a polymerizable compound, "NCI-930" (O-acyl oxime compound) of Ai Dike (ADEKA) company as a polymerization initiator, 1.53 parts by mass of "FTX-218D" (fluorine-based surfactant) of Naors (NEOS) company as a surfactant, 0.31 parts by mass of "Karenz (Karenz) MT PE1" (multifunctional thiol) of Showa electric company as a reaction regulator, 0.10 parts by mass of "Yi Lunuo Six (Irganox) 1010" (phenol antioxidant) of Basf company as an antioxidant, and 25 parts by mass of cyclopentanone (CPone) as an antioxidant were measured, and mixed by a stirring solvent using a stirring machine. About 100mL of the mixture was subjected to pressure filtration using a 0.5 μm Polytetrafluoroethylene (PTFE) filter under a certain pressure of 0.05MPa, thereby obtaining a composition of example 1.

Examples 2 to 13 and comparative examples 1 to 3

Except for the total amount and blending amount (parts by mass) of the dispersion, the pigment solution and the binder resin solution, and the polymerizable compoundThe 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 blending amounts (parts by mass) of the polymer, the polymerization initiator, the surfactant, the reaction modifier, the antioxidant and the solvent were as shown in table 1. Table 1 also shows [ A ] in each of the obtained compositions]Phthalocyanine compounds, [ 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 _0.33 WO ₃ )。

[ evaluation ]

The following evaluations were performed using the respective compositions obtained. The evaluation results are shown in table 1.

Each composition was applied on the glass substrate by spin coating so as to have a predetermined film thickness. Thereafter, the coating film was heated at 100℃for 120 seconds, and was made 500mJ/cm by an i-ray stepper ² Exposure is performed by way of (a) a pattern. Then, by heating at 220℃for 300 seconds, an infrared shielding film having an average film thickness of 2.0 μm to 4.0 μm was produced on the glass substrate. The average film thicknesses are shown in table 1. Further, the film thickness was measured by a stylus type Step-difference meter (α Step IQ of large and scientific company). Next, transmittance in each wavelength region of the infrared shielding film formed on the glass substrate was measured by comparison with the glass substrate using a spectrophotometer (japanese spectroscopy "V-7300"). Based on the obtained spectrum, evaluation was performed based on the evaluation criteria described below.

(visible light transmittance)

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

A:80% or more

B:70% or more and less than 80%

C: less than 70%

(visible transmission window range)

The transmittance in the range of 430nm to 580nm was found to be 70% or more continuously. When the continuous range is 70% or more and 175nm or more, the infrared shielding film has high sensitivity and therefore is expected to be highly practical when used as an infrared shielding film. The visible light transmission window range was evaluated by the following criteria.

A:200nm or more

B:175nm or more and less than 200nm

C: less than 175nm

(Infrared shielding Range)

The transmittance in the range of 700nm to 800nm was continuously in the range of 20% or less. When the continuous range of 20% or less is 20nm or more, the infrared shielding film has a high noise shielding function and is therefore expected to have high practical applicability. The infrared shielding range was evaluated by the following criteria.

A:30nm or more

B:20nm or more and less than 30nm

C: less than 20nm

(average deviation (Off-Slope))

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

(Z)＝60/((Y)-(X))

AA:0.60 or more

A: more than 0.50 and less than 0.60

B: more than 0.45 and less than 0.50

C: less than 0.45

(Heat resistance)

The infrared shielding film formed 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 contrast with the glass substrate using a spectrophotometer (Japanese Spectrophotometer "V-7300"). At this time, the absorbance of the produced infrared shielding film at the wavelength at which the transmittance was lowest in the range of 700nm to 800nm was (A1), the absorbance after heating at 260 ℃ at the same wavelength was (A2), and the absorbance retention=100× (A1)/(A2), and the heat resistance at 260 ℃ was evaluated using 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 is used in combination with a protective film or the like, and high heat resistance can be maintained, and the practical use is high. The retention rate was evaluated using the following criteria.

AA:90% or more of

A: more than 60 percent and less than 90 percent

B: more than 30 percent and less than 60 percent

C: less than 30%

(defect suppression)

Each composition was applied to a silicon substrate by spin coating, and the coating film was cured to form a cured film having a film 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, KLA-Tencor, KLA). It can be determined that the smaller the value of the defect density is, the higher the defect suppression is. The defect means a detection point having a size of 1 μm or more. Based on the defect density, defect suppression was evaluated using the following criteria.

A：10/cm ² The following are the following

B: exceeding 10/cm ² And is 50/cm ² The following are the following

C: exceeding 50/cm ²

(delay after coating (Post Coating Delay, PCD) stability)

Each composition was applied to a silicon substrate by spin coating, and a coating film having a film thickness of about 1 μm was formed without hardening the coating film. The Defect density (Defect density) of the coating film was measured using a Defect/foreign matter inspection apparatus (KLA 2351 of KLA-Tencor). Then, the defect density of the coating film was measured at regular intervals, the time in which the defect number was increased by 20% or more from the initial value was measured, and the stability of the coated film after the coating (PCD: post Coating Delay) was evaluated by the following criteria. Regarding PCD stability, the greater the extrapolated value, the higher the utility.

A: for more than 24 hours

B: over 12 hours and less than 24 hours

C: less than 12 hours

As shown in table 1, the visible light transmittance window range, the infrared shielding range, the average Off-Slope, the heat resistance, the defect suppression property, and the PCD stability of examples 1 to 13 were all evaluated well. It is also found that, in each example 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 R have higher heat resistance than example 2 using the phthalocyanine compound (a-2) having no substituent R. In the examples using the phthalocyanine compound having a substituent R, the visible light transmittance of examples 1, 3 and 4 was also found to be good.

Industrial applicability

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

Claims

1. A composition for an optical sensor comprising:

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

the binder resin is used in the form of a binder resin,

in the formula (1), each of the plurality of R is independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; each of the plurality of X's is independently a hydrogen atom, a halogen atom or an alkyl group; multiple X's may also be bonded to each other and form an aromatic ring together with the carbon chains to which they are bonded; m is VO; the plurality of n are 4 respectively.

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

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

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

5. The composition for an optical sensor according to claim 1 or 2, wherein the substituents of the alkyl group and the aryl group each of which is represented by R are groups having a heteroatom.

6. The composition for an optical sensor of claim 5, wherein the substituent is a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, or a combination thereof.

7. The composition for an optical sensor according to claim 1 or 2, further comprising an infrared shielding agent,

the infrared shielding agent is a metal oxide, a copper compound, or a combination thereof, with the exception that the copper compound is the phthalocyanine compound.

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

9. A composition for optical sensors, which comprises a phthalocyanine compound represented by the following formula (2):

in the formula (2), each of the plurality of R is independently an alkyl group having a substituent or an aryl group having a substituent; each of the plurality of X's is independently a hydrogen atom, a halogen atom or an alkyl group; multiple X's may also be bonded to each other and form an aromatic ring together with the carbon chains to which they are bonded; m is VO; the plurality of n are 4 respectively.

10. The composition for an optical sensor according to claim 9, wherein the substituents of the alkyl group and the aryl group each of which is represented by R are groups having a heteroatom.

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

12. The composition for an optical sensor according to any one of claim 9 to 11, further comprising an infrared shielding agent,

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