JPWO2020071486A1 - Composition for optical sensor - Google Patents

Abstract

Provided is a composition for an optical sensor capable of forming an optical filter for an optical sensor having good properties regarding visible light transmission and infrared shielding property. The present invention is a composition for an optical sensor containing a phthalocyanine compound represented by the following formula (1) and a binder resin. In the formula (1), each of the plurality of Rs is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group, respectively. Each of the plurality of Xs is independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. The plurality of ns are independently integers of 3 to 6.

Description

The present invention relates to compositions for optical sensors.

Video cameras, digital cameras, mobile phones with camera functions, and the like are equipped with a solid-state image sensor, which is an optical sensor. As the solid-state image sensor, specifically, a CCD (Charge-Coupled Device) image sensor, a CMOS (Complementary MOS) image sensor, and the like are known. The sensitivity of the photodiode provided in these solid-state image sensors ranges from the visible light region to the infrared region. For this reason, the solid-state image sensor is provided with a filter for blocking infrared rays. With this optical filter (infrared blocking filter), the sensitivity of the solid-state image sensor can be corrected so as to approach the human visual sensitivity. Similarly, an optical sensor other than the solid-state image sensor may be provided with a filter for blocking infrared rays.

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

Japanese Unexamined Patent Publication No. 2008-201952

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 ray shielding property, and the like of the optical filter. Further, when forming an infrared shielding film of an optical filter by coating a composition containing a dye such as a phthalocyanine compound, if the infrared shielding film is left for a long time after coating, defects such as foreign substances are likely to occur in the obtained infrared shielding film. .. In the production process, it is desired that an infrared shielding film having few defects such as foreign substances can be obtained even if it is left to stand for a while after coating and then cured.

Further, the conventional optical filter is not sufficiently satisfied with the visible light transmission property and the infrared ray shielding property. Specifically, when an optical filter is used as an infrared blocking filter for an optical sensor such as a solid-state imaging device, it not only has high visible light transmittance and low infrared transmittance, but also has a high visible light transmittance in the wavelength region. It is required that the wavelength region having low infrared transmittance is wide and that the wavelength region having high visible light transmittance and the wavelength region having low infrared transmittance are close to each other. When an optical filter having such characteristics is used for an optical sensor such as a solid-state image sensor, sensitivity, noise shielding function, color reproducibility, and the like can be improved.

The present invention has been made based on the above circumstances, and an object of the present invention is to provide an optical filter for an optical sensor, which has few defects such as foreign substances and has good characteristics regarding visible light transmission and infrared shielding property. It is to provide the composition for an optical sensor which can be formed.

（式（１）中、複数のＲは、それぞれ独立して、置換基を有する若しくは非置換のアルキル基、又は置換基を有する若しくは非置換のアリール基である。複数のＸは、それぞれ独立して、水素原子、ハロゲン原子又はアルキル基である。複数のＸは、互いに結合してこれらが結合する炭素鎖と共に芳香環を形成していてもよい。Ｍは、２つの水素原子、２価の金属原子、又は３若しくは４価の金属原子の誘導体である。複数のｎは、それぞれ独立して、３〜６の整数である。）The invention made to solve the above problems is a composition for an optical sensor containing a phthalocyanine compound represented by the following formula (1) and a binder resin.

(In the formula (1), each of the plurality of Rs is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group. The plurality of Xs are independent of each other. A plurality of Xs may be bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. M is two hydrogen atoms and divalent. It is a metal atom or a derivative of a trivalent or tetravalent metal atom. A plurality of ns are independently integers of 3 to 6).

（式（２）中、複数のＲは、それぞれ独立して、置換基を有するアルキル基、又は置換基を有するアリール基である。複数のＸは、それぞれ独立して、水素原子、ハロゲン原子又はアルキル基である。複数のＸは、互いに結合してこれらが結合する炭素鎖と共に芳香環を形成していてもよい。Ｍは、２つの水素原子、２価の金属原子、又は３若しくは４価の金属原子の誘導体である。複数のｎは、それぞれ独立して、３〜６の整数である。）Another invention made to solve the above problems is a composition for an optical sensor containing a phthalocyanine compound represented by the following formula (2).

(In the formula (2), a plurality of Rs are independently alkyl groups having a substituent or an aryl group having a substituent. A plurality of Xs are independently hydrogen atoms, halogen atoms or or. It is an alkyl group. A plurality of Xs may be bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. M is a two hydrogen atom, a divalent metal atom, or a trivalent or tetravalent group. It is a derivative of the metal atom of. A plurality of n are independently integers of 3 to 6).

According to the present invention, it is possible to provide an optical sensor composition capable of forming an optical filter for an optical sensor having few defects such as foreign substances and having good characteristics regarding visible light transmission and infrared shielding property. ..

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 composition (I) for an optical sensor according to an embodiment of the present invention (hereinafter, also simply referred to as “composition (I)”) contains a [A1] phthalocyanine compound and a [B] binder resin. The composition preferably further contains a metal oxide, a copper compound (excluding the [A] phthalocyanine compound), or a combination thereof, [C] an infrared shielding agent.

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

In the formula (1), each of the plurality of Rs is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group, respectively. Each of the plurality of Xs is independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs may be bonded to each other to form an aromatic ring together with the carbon chains to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. The plurality of ns are independently integers of 3 to 6.

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

Examples of the aryl group represented by R include a monovalent group composed of only an aromatic ring and a monovalent group in which an alkyl group is bonded to the aromatic ring. Specific examples of the aryl group represented by R include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthracenyl group and the like. As the aryl group, a group composed of only an aromatic ring is preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is further preferable from the viewpoint of visible light transmission and the like.

The R is preferably an aryl group having a substituent or an unsubstituted group from the viewpoint of heat resistance of the obtained optical filter and the like.

The alkyl group and aryl group represented by each of the plurality of Rs may or may not have a substituent, but preferably have a substituent. That is, it is preferable that the plurality of Rs are independently an alkyl group having a substituent or an aryl group having a substituent. As described above, when the plurality of Rs have substituents, the compatibility of the [A1] phthalocyanine compound is further enhanced, defects such as foreign substances in the obtained optical filter are further suppressed, and visible light transmittance and infrared shielding property are further suppressed. The properties related to are also better. Further, when the plurality of Rs have substituents, the heat resistance of the obtained optical filter is also improved.

The substituent that can be possessed by the alkyl group and the aryl group represented by the plurality of Rs, respectively, may be a hydrocarbon group such as an alkenyl group or an alkynyl group, but may be a group having a hetero atom. preferable. Heteroatom refers to an atom other than a hydrogen atom and a carbon atom. Since the alkyl group and the aryl group represented by the plurality of Rs each have a substituent having a heteroatom, the compatibility and the like are further enhanced, defects such as foreign substances in the obtained optical filter are further suppressed, and visible light is obtained. The properties related to transparency and infrared shielding are also improved. Further, when the plurality of Rs have a substituent having a hetero atom, the heat resistance of the obtained optical filter is also improved. As the hetero atom, a halogen atom, an oxygen atom and a sulfur atom are preferable, and a halogen atom and an oxygen atom are more preferable.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom is preferable.

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

The alkylthio group, a methylthio group _(CH 3 -S-), ethylthio group _(-S- C ₂ H 5), can be exemplified propylthio _{(C 3} H 7 -S-) such as methylthio group and ethylthio group Is more preferable.

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, it is also preferable that it is a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group or a combination thereof.

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

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

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

The plurality of Xs may be coupled to each other. Usually, of a plurality of Xs, two Xs bonded to the same benzene ring are bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. Examples of the aromatic ring formed include a benzene ring, a naphthalene ring, an anthracene ring and the like. The hydrogen atoms of these aromatic rings may be substituted with hydrocarbon groups or other substituents.

As the X, a hydrogen atom is preferable. Further, the plurality of Xs 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, and Pb. The divalent metal atom means a metal atom that can become a divalent cation.

Here, the derivative of a metal atom means an atomic group containing a metal atom. A trivalent metal atom is a metal atom that can become a trivalent cation. Examples of the trivalent metal atom include Al and In. A tetravalent metal atom is a metal atom that can become a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, Sn and the like. The metal atom also includes a metalloid atom. Derivatives of the trivalent or tetravalent metal atom represented by M are 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 and the like can be mentioned.

As the M, H ₂ (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO and TiO are preferable, and VO is more preferable.

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

[A1] The lower limit of the maximum absorption wavelength of the phthalocyanine compound is preferably 680 nm, more preferably 700 nm, and even more preferably 720 nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000 nm, more preferably 900 nm, further preferably 800 nm, and even more preferably 750 nm. [A1] When the maximum absorption wavelength of the phthalocyanine compound is in the above range, it is possible to form an optical filter having better characteristics regarding visible light transmission and infrared shielding property.

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

In formulas (i) and (ii), R, X and n are synonymous with those in 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 their halides and carboxylates. , Sulfates, nitrates, carbonyl compounds, oxides, complexes and the like. Among these, metal halides and carboxylates are particularly preferably used. Examples of these are copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, iron chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, oxy. Examples thereof include vanadium chloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.

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

Examples of organic solvents used are methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, n-hexanol, 1-heptanol, 1-octanol, 1-dodecanol, benzyl alcohol, ethylene. Alcohol solvents such as glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylethanol, diethylethanol, dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, DMI (1,3-dimethyl-2-imidazole) High boiling point solvents such as lysine) and urea can be mentioned.

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

In the case of a phthalocyanine compound in which M in the formula (1) is two hydrogen atoms, a phthalocyanine compound represented by the formula (i) or a 1,3-diiminoison indolin compound represented by the formula (ii). It can be produced by reacting a compound with metallic sodium or metallic potassium under the above reaction conditions, and then desorbing the central metal sodium or potassium with hydrochloric acid, sulfuric acid or the like.

After 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 to obtain the phthalocyanine compound represented by the formula (1). be able to. If necessary, the desired product having higher purity can be obtained by further purifying by a known purification method such as recrystallization or column chromatography.

The phthalonitrile-based compound represented by the formula (i) and the 1,3-diimiminoisone indoline-based compound represented by the formula (ii) can be synthesized with reference to known methods. For example, it can be synthesized with reference to the method described in Special Table 2003-516421.

The lower limit of the content of the [A1] phthalocyanine compound in the total solid content (all components other than the solvent) in the composition (I) is preferably 0.1% by mass, more preferably 0.5% by mass, and 1 By mass% is even more preferred, and 2% by mass is even more preferred. On the other hand, as the upper limit of this content, 30% by mass is preferable, 15% by mass is more preferable, 10% by mass is further preferable, and 8% by mass is more preferable. [A1] By setting the content of the phthalocyanine compound in the above range, the characteristics related to the visible light transmittance and the infrared ray shielding property of the obtained optical filter become better.

[A1] As the phthalocyanine compound, one type may be used alone, or two or more types may be used in combination.

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

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

Examples of the monomer giving a structural unit containing a polymerizable group include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3, 4 epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate and 3-methacryloxypropyl triethoxysilane.

Further, for example, by reacting a resin having a structural unit having a carboxy group with a compound having a group (oxylanyl group, oxetanyl group, etc.) that reacts with the carboxy group and a polymerizable group such as a (meth) acryloyl group. Also, structural units containing polymerizable groups 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, and 15% by mass with respect to 100% by mass of the [B] binder resin. More preferably, 30% by mass, 50% by mass or 75% by mass may be even more preferable. On the other hand, as the upper limit of this content, 95% by mass is preferable, 90% by mass is more preferable, and 85% by mass is further preferable.

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

Examples of the monomer that gives a structural unit containing a ring structure to the main chain include N-substituted maleimide-based monomers and cycloolefins.

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

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

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

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

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

Examples of the monomer giving a structural unit containing an acidic group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; malein. Unsaturated dicarboxylic acids such as acids, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof; monosuccinic acid [2- (meth) acryloyloxyethyl] , Mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as mono [2- (meth) acryloyloxyethyl]; such as ω-carboxypolycaprolactone mono (meth) acrylate. Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends.

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% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on 100% by mass of the [B] binder resin. Is.

[B] The binder resin can further contain other structural units. Examples of the monomer giving other structural units include aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene.
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2- 10) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (Meta) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (Meta) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) (Meta) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane,
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ,
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains 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 and the like by a known method. Further, the binder resin [B] may be used alone or in combination of two or more.

[B] The polystyrene-equivalent weight average molecular weight (Mw) of the binder resin is preferably 2,000 to 500,000, more preferably 3,000 to 100, as measured by the gel permeation chromatography (GPC) method. It is 000, more preferably 4,000 to 30,000. When Mw is in the above range, a [B] binder resin having excellent solubility in a solvent or a developing solution and having sufficient mechanical properties can be obtained.

The lower limit of the content of the [B] binder resin in the total solid content of the composition (I) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass. On the other hand, as the upper limit of this content, 70% by mass is preferable, 60% by mass is more preferable, and 50% by mass is further preferable. By setting the content of the binder resin in the above range, the heat resistance and the like can be improved while sufficiently exhibiting the characteristics related to the visible light transmittance and the infrared ray shielding property of the obtained optical filter.

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

[C] Examples of the metal oxide as an infrared shielding agent include tungsten oxide compounds, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), and zirconia (Zirconia). ZrO ₂ ), spinel (MgAl ₂ O ₄ ) and the like can be mentioned.

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

[C] As the infrared shielding agent, a metal oxide is preferable, and a tungsten oxide-based compound is more preferable. Tungsten oxide compounds are infrared shields that have high absorption (that is, high shielding against infrared rays) for infrared rays (particularly infrared rays with a wavelength of about 800 nm or more and 1200 nm or less) and low absorption for visible light. be. Therefore, when the composition (I) contains a tungsten oxide-based compound, it is possible to improve the infrared shielding property while maintaining the good visible light transmittance of the obtained optical filter. [C] As the infrared shielding agent, one type may be used alone, or two or more types may be mixed and used.

The tungsten oxide-based compound is more preferably a tungsten oxide-based compound represented by the following formula (3).
A _x W _oy ... (3)

In formula (3), A is a metallic element. 0.001 ≦ x ≦ 1.1. 2.2 ≦ y ≦ 3.0.

Examples of the metal element represented by A in the above formula (3) include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, and 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.

As the above A, an alkali metal is preferable, Rb and Cs are more preferable, and Cs is further preferable. That is, the metal oxide is more preferably tungsten cesium oxide.

When x in the above 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, it is possible to more reliably avoid the formation of an impurity phase in the tungsten oxide-based compound. The upper limit of x is preferably 1 and more preferably 0.5.

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

Specific examples of the tungsten oxide compound represented by the above formula (3) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Ba _0.33 WO _3. Cs _0.33 WO ₃ and Rb _0.33 WO ₃ are preferable, and Cs _0.33 WO ₃ is more preferable.

[C] The infrared shielding agent is preferably fine particles. [C] The upper limit of the average particle size (D50) of the infrared shielding agent is preferably 500 nm, more preferably 200 nm, further preferably 50 nm, and even more preferably 30 nm. When the average particle size is not more than the above upper limit, the visible light transmission can be further enhanced. On the other hand, for reasons such as ease of handling during manufacturing, the average particle size of the [C] infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

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

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

As 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, 1 is preferable, 2 is preferable, and 3 is more preferable. On the other hand, as the upper limit of this mass ratio ([C] / [A1]), 40 is preferable, 20 is more preferable, and 10 is further preferable. By setting the content ratio of the [A1] phthalocyanine compound and the [C] infrared shielding agent within the above range, the characteristics of the obtained optical filter with respect to visible light transmission and infrared shielding are further improved.

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

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

[D] Dispersants are commercially available, for example, as (meth) acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK). ), As urethane dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (all manufactured by Big Chemie (BYK)). 76500 (manufactured by Lubrizol Co., Ltd.), Solsparse 24000 (manufactured by Lubrizol Co., Ltd.) as a polyethyleneimine-based dispersant, Ajispar PB821, Ajispar PB822, Ajispar PB880, Ajispar PB881 (above, In addition to Ajinomoto Fine-Techno Co., Ltd.), BYK-LPN21324 (manufactured by Big Chemie (BYK)) and the like can be mentioned.

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

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

([E] Polymerizable compound)
The composition (I) preferably further contains the [E] polymerizable compound. When the composition (I) contains the [E] polymerizable compound, good curability and good heat resistance of the obtained optical filter can be exhibited. [E] The polymerizable compound means a compound having two or more polymerizable groups. The [B] binder resin having two or more polymerizable groups is not included in the [E] polymerizable compound. Examples of the polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. [E] As the polymerizable compound, a compound having two or more (meth) acryloyl groups and a compound having two or more N-alkoxymethylamino groups are preferable, and the compound has two or more (meth) acryloyl groups. Compounds are more preferred. [E] The polymerizable compound may be used alone or in admixture of two or more.

Examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a caprolactone-modified polyfunctional (meth) acrylate. , Alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having a hydroxyl group and polyfunctional isocyanate, (meth) acrylate having a hydroxyl group and acid anhydride. Examples thereof include a polyfunctional (meth) acrylate having a carboxyl group, which is a reaction product with and the like.

Here, examples of the above-mentioned aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, and glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Aliphatic polyhydroxy compounds having a trivalent or higher valence can be mentioned. 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. And so on. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydride include anhydrides of dibasic acids such as oxalic anhydride, maleic anhydride, glutacon anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. Examples thereof include tetrabasic acid dianhydrides such as acid dianhydrides and benzophenone tetracarboxylic acid dianhydrides.

Specific examples of the compound having two or more (meth) acryloyl groups include, for example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1 , 9-Nonandiol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclode Candi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol tri ( Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipenta Examples thereof include erythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and urethane (meth) acrylate compound.

Among the compounds having two or more (meth) acryloyl groups, a polyfunctional (meth) acrylate is preferable, and a polyfunctional (meth) acrylate having three or more and ten 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-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Specific examples of compounds having two or more N-alkoxymethylamino groups include N, N, N', N', N'', N''-hexa (alkoxymethyl) melamine, N, N, N'. , N'-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluryl 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 even more preferably 20% by mass. On the other hand, as the upper limit of this content, 60% by mass is preferable, 50% by mass is more preferable, and 40% is further more preferable.

([F] Polymerization Initiator)
The composition (I) preferably contains the [F] polymerization initiator. [F] Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but a photopolymerization initiator is preferable. This makes it possible to impart photosensitivity (radiation sensitivity) to the composition (I). The photopolymerization initiator refers to a compound that generates an active species capable of initiating polymerization of the [E] polymerizable compound or the like by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. [F] The polymerization initiator may be used alone or in admixture of two or more.

[F] Examples of the polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-diketones. Examples thereof include system compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds and the like. Among these, thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds and O-acyloxime-based compounds are preferable, and O-acyloxime-based 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 acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane. Examples thereof include -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4). -Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole and the like can be mentioned.

When a biimidazole compound is used, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like. Amine-based hydrogen donors can be mentioned.

Examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of JP-A-57-6096 and JP-A-2003-23898.

Examples of O-acyloxime compounds include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and ethanone-1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H -Carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF), etc. may be used. can.

When a photopolymerization initiator is used, a sensitizer may also be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethylamino. Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

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, more preferably 3% by mass. On the other hand, the upper limit of this content is preferably 30% by mass, more preferably 10% by mass.

(Other organic pigments)
The composition (I) may contain a known organic dye other than the organic dye as the [A1] phthalocyanine compound and the [B] copper compound which is an infrared shielding agent. Other organic dyes include diminium compounds, squarylium compounds, cyanine compounds, naphthalocyanine compounds, quaterylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrolopyrrole compounds, oxonor compounds, croconium compounds, hexaphyllin. Examples include compounds (excluding those containing a copper atom). Further, a phthalocyanine compound other than the [A1] phthalocyanine compound and the [B] phthalocyanine compound as an infrared shielding agent can also be used.

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”). [A] The lower limit of the maximum absorption wavelength of the phthalocyanine compound is preferably 600 nm, more preferably 650 nm. On the other hand, the upper limit of the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 900 nm, more preferably 850 nm, further preferably 800 nm, and even more preferably 750 nm. The lower limit of the difference between the maximum absorption wavelength of the [A1] phthalocyanine compound and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm. On the other hand, the upper limit of this difference is preferably 100 nm, more preferably 80 nm, and even more preferably 60 nm. [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 dye in the composition (I) is preferably 50% by mass, more preferably 70% by mass, more preferably 80% by mass, and 90% by mass. % May be more preferred, and 99% by weight may be more preferred. As the organic dye, it may be preferable to substantially contain only the [A1] phthalocyanine compound. The composition (I) can be increased in productivity by reducing the content of other organic dyes in this way.

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

Examples of the additive include a surfactant, an adhesion accelerator, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, a residue improving agent, a developability improving agent, a reaction adjusting agent and the like.

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

Adhesion promoters 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) ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane.

Antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-). 4-Hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2, 4,8,10-Tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned. The content of the antioxidant may be 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-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and the like.

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

Residue improvers 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- Examples thereof include 1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like.

Developable agents include succinate mono [2- (meth) acryloyloxyethyl], phthalate mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like. Can be mentioned.

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

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

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

Examples of such a 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, and diethylene glycol mono-n-. Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) Alkylene glycol monoalkyl ethers,
Lactic acid alkyl esters such as methyl lactate and ethyl lactate,
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol, etc.
Keto alcohols 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, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate,
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.
Chain ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, and ketones such as cyclic ketones such as cyclopentanone and cyclohexanone,
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, etc.
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate, etc. ,
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i butyrate Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc.
Aromatic hydrocarbons such as toluene and xylene,
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and lactams.

The content of the solvent in the composition (I) is not particularly limited. The lower limit of the solid content concentration (total concentration of each component excluding the solvent) in the composition (I) is preferably 5% by mass, more preferably 10% by mass. On the other hand, the upper limit of the solid content concentration is preferably 50% by mass, more preferably 40% by mass. By setting the solid content concentration in the above range, the dispersibility, stability, coatability and the like become better.

(Preparation method)
The method for preparing the composition (I) is not particularly limited, and it can be prepared by mixing each component. For example, when the composition contains a metal oxide as a [C] infrared shielding agent and a [D] dispersant, first, a dispersion containing a [C] infrared shielding agent, a [D] dispersant and a solvent. A method of preparing a liquid, adding [A1] phthalocyanine compound, [B] binder resin, and other components as necessary to the dispersion and mixing them can be adopted. The dispersion liquid or the composition (I) can be subjected to a filtration treatment, if necessary, to remove agglomerates.

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

In the formula (2), each of the plurality of Rs is an alkyl group having a substituent or an aryl group having a substituent, respectively. Each of the plurality of Xs is independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs may be bonded to each other to form an aromatic ring together with the carbon chains to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. The plurality of ns are independently integers of 3 to 6.

The [A2] phthalocyanine compound is the same as the above-mentioned [A1] phthalocyanine compound, except that the plurality of Rs are independently an alkyl group having a substituent or an aryl group having a substituent. The preferred form of the [A2] phthalocyanine compound is also the same as that of the above-mentioned [A1] phthalocyanine compound.

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

<Infrared shielding film>
From the composition (I) and the composition (II) according to the embodiment of the present invention (hereinafter, the composition (I) and the composition (II) are collectively referred to as simply "composition"), an optical filter is used. Infrared shielding film for use can be formed. This infrared shielding film has few defects such as foreign substances, and has good properties regarding visible light transmittance and infrared shielding property.

The infrared shielding film can be formed by, for example, the following method. First, the composition is applied onto the support, and then prebaked to evaporate the solvent to form a coating film. Next, after exposing this coating film, it is developed with a developing solution to dissolve and remove the unexposed portion of the coating film. Then, by post-baking, an infrared shielding film (I) patterned in a predetermined shape is obtained. When the composition does not contain the [E] polymerizable compound and the [F] polymerization initiator, it is not necessary to perform a curing treatment such as exposure. Further, it is not necessary to perform the developing process, and in this case, an infrared shielding film that is not patterned can be formed.

The transparent substrate, microlens, color filter and the like correspond to the support to which the composition is applied. For the above coating, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), and a bar coating method can be adopted.

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

Examples of the light source of radiation used for exposing the coating film include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, argon ion lasers, and YAG lasers. Examples thereof include a laser light source such as an XeCl excimer laser and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 nm or more and 450 nm or less. Exposure of radiation, typically on the order 10J / ^{m 2} or more 50,000J / ^{m 2} or less.

As the developer, an alkaline developer is generally used. Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonen or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After development, it is usually washed with water.

As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied. The developing conditions are about 5 seconds or more and 300 seconds or less at room temperature.

The conditions for post-baking are usually 180 ° C. or higher and 280 ° C. or lower, and 1 minute or longer and 60 minutes or lower.

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

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

The optical filter may be composed of only the infrared shielding film, or may be composed of 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 in an optical sensor such as a solid-state image sensor as one component. In this case, the infrared shielding film alone functions as an optical filter (infrared cut filter). It is preferable that the infrared shielding film is incorporated in the optical sensor because a large process margin can be obtained. The infrared shielding film (when incorporated in the solid-state image sensor, the infrared shielding film is, for example, on the outer surface side of the microlens of the solid-state image sensor, between the microlens and the color filter, and between the color filter and the photodiode. 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, a transparent resin, or the like is adopted. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Such an optical filter is also suitably used as an infrared cut filter or the like in a solid-state image sensor.

Optical sensors such as solid-state image sensors equipped with the above optical filters are used in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, mobile information terminals, personal computers, video games, medical devices, etc. It is useful.

<Optical sensor>
The optical filter is used for an optical sensor such as a solid-state image sensor. Since the optical filter has few defects such as foreign substances and has good characteristics regarding visible light transmission and infrared shielding property, an optical sensor such as a solid-state image sensor having the optical filter has high sensitivity, color reproducibility, and the like. Excellent in practicality.

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

In the solid-state image sensor, the optical filter (infrared shielding film) is formed on the outer surface side of the microlens, between the microlens and the color filter, and a layer on which the color filter and the plurality of photodiodes are arranged. It can be provided in between. The optical filter is preferably laminated between the microlens and the color filter or between the color filter and the photodiode. Further, another layer (flattening layer or the like) may be provided between the optical filter and the microlens, color filter, photodiode or the like.

Specific examples of the solid-state image sensor include CCD and CMOS as camera modules. The solid-state image sensor is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, mobile information terminals, personal computers, video games, medical devices, and the like.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Synthesis Example 1> Synthesis of phthalocyanine compound (a-1) 4,7-bis (4- (2,6-dimethoxyphenoxy) butyl) -1,3-diiminoisoindoline 32.9 g, vanadium trichloride 4. 76 g and 13.74 g of DBU were stirred in 100 mL of 1-pentanol at an internal temperature of 125 ° C. for 24 hours. Then, 600 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (silica gel / toluene) gave 11.2 g of green powder. From the analysis results below, it was confirmed that the obtained compound was the target compound (a-1) represented by the following formula (a-1).
・ MS: (EI) m / z 2245M +)
-Elemental analysis value: Measured value (C: 68.44%, H: 6.44%, N: 4.99%);
Theoretical value (C: 68.47%, H: 6.46%, N: 4.99%)
The toluene solution of the compound thus obtained showed maximum absorption at 734.5 nm, and the gram extinction coefficient was 6.75 × 10 ⁴ mL / g · cm.

なお、上記式中、「＊」は、結合手を示す（以下の化学式においても同様）。

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

<Synthesis Example 2> Synthesis of phthalocyanine compound (a-2) Instead of 4,7-bis (4- (2,6-dimethoxyphenoxy) butyl) -1,3-diiminoisoindoline 32.9 g in Synthesis Example 1. 14.5 g of green powder was obtained in the same manner as in Synthesis Example 1 except that 18.6 g of 4,7-bis (4-methoxybutyl) -1,3-diiminoisoindoline was used. From the analysis results below, it was confirmed that the obtained compound was the target compound (a-2) represented by the following formula (a-2).
・ MS: (EI) m / z 1267M +)
-Elemental analysis value: Measured value (C: 68.20%, H: 7.66%, N: 8.82%);
Theoretical value (C: 68.17%, H: 7.63%, N: 8.83%)
Toluene solution of the compound obtained in this way showed a maximum absorption at 734.0nm, gram absorption coefficient was ^{1.21 × 10 5 mL / g ·} cm.

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

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

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

<Synthesis Example 6> Synthesis of phthalocyanine compound (a-6) Instead of 4,7-bis (4- (2,6-dimethoxyphenoxy) butyl) -1,3-diiminoisoindoline 32.9 g in Synthesis Example 1. 4,7-Bis (4-((1,6-dimethoxynaphthalen-2-yl) oxy) butyl) -1,3-diiminoisoindoline 19.4 g and 4,7-bis (4- (2,2,2) 6-Dimethoxyphenoxy) Butyl) -1,3-Diiminoisoindoline 28.1 g was obtained in the same manner as in Synthesis Example 1 except that 16.5 g was used. It was confirmed by LC-MS that the obtained compound was the target compound (a-6) represented by the following formula (a-6) by matching the m / z of each component.
The toluene solution of the compound thus obtained showed maximum absorption at 735.5 nm, and the gram extinction coefficient was 6.30 × 10 ⁴ mL / g · cm.

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

<Synthesis Example 7> Synthesis of Phthalocyanine Compound (a'-1) According to the description of Example (65) of JP-A-02-138382, phthalocyanine (a'-1) for comparative examples represented by the following formula (a'-1) ( Maximum absorption wavelength 725 nm) was synthesized.

<Synthesis Example 8> Synthesis of Phthalocyanine Compound (a'-2) For Comparative Examples represented by the following formulas using the method described in paragraph [0075] (Example 4) of JP-A-2016-204536. A phthalocyanine compound (a'-2) (maximum absorption wavelength 728 nm) was synthesized.

<Synthesis Example 9> Synthesis of Phthalocyanine Compound (a'-3) Other dyes represented by the following formulas using the methods described in paragraphs [0020] to [0025] (Example 1) of JP-A-05-25177. Phthalocyanine compound (a'-3) (maximum absorption wavelength 692 nm) was synthesized.

<Synthesis Example 10> Synthesis of Tungsten Tungsten Trioxide Powder A tungsten cesium oxide (Cs _0.33 WO ₃ ) powder was synthesized by using the method described in paragraph [0113] of Japanese Patent No. 4096205.

<Synthesis Example 11> Synthesis of binder resin (b-1) 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, 2-ethylhexyl methacrylate in a reaction vessel. 29 parts by mass and 20 parts by mass of methacrylic acid were dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate, and 3 parts by mass of 2,2'-azoisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were further added. After purging the inside of the reaction vessel with nitrogen, the mixture is heated at 80 ° C. for 5 hours while stirring and bubbling nitrogen to prepare a solution containing the binder resin (b-1) (binder resin solution (B-1): solid content concentration 35% by mass). Obtained. The obtained binder resin (b-1) was obtained by combining three LF-604 manufactured by Showa Denko Corporation and KF-602 with a gel permeation chromatography (GPC) apparatus (GPC-104 type, column: Showa Denko Corporation). When the polystyrene-equivalent molecular weight was measured using (developing solvent: tetrahydrofuran), the weight average molecular weight (Mw) was 9700, the number average molecular weight (Mn) was 5700, and Mw / Mn was 1.70. In this synthesis example, the charging ratio (mass ratio) of each monomer and the content ratio (mass ratio) of the structural units derived from each monomer in the obtained binder resin are substantially the same. (The same applies to the following synthesis example 14).

<Synthesis Example 12> Synthesis of Binder Resin (b-2) 200 parts by mass of propylene glycol monomethyl ether was placed in a flask equipped with a cooling tube and a stirrer, and the temperature was raised to 80 ° C. At the same temperature, a mixed solution of 100 parts by mass of propylene glycol monomethyl ether, 100 parts by mass of methacrylic acid, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours, and the temperature was maintained after the addition. It was polymerized for 3 hours. Then, the temperature of the reaction solution was raised to 100 to 120 ° C., 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 are added, and the temperature is raised to 110 ° C. for 9 hours. A solution containing the binder resin (b-2) represented by (binder resin solution (B-2): solid content concentration 40% by mass) was obtained. When the molecular weight of the obtained binder resin was measured in the same manner as in Synthesis Example 11, the weight average molecular weight (Mw) was 15100, the number average molecular weight (Mn) was 7000, and Mw / Mn was 2.16.

（上記式において、組成比は質量比である。）

(In the above formula, the composition ratio is the mass ratio.)

<Synthesis Example 13> Synthesis of Binder Resin (b-3) 200 parts by mass of propylene glycol monomethyl ether was placed in a flask equipped with a cooling tube and a stirrer, and the temperature was raised to 80 ° C. At the same temperature, a mixed solution of 200 parts by mass of propylene glycol monomethyl ether, 67 parts by mass of methacrylic acid, 33 parts by mass of N-cyclohexyl maleimide, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours. After dropping, the temperature was maintained and polymerization was carried out for 3 hours. Then, the temperature of the reaction solution was raised to 100 to 120 ° C., 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 are added, the temperature is raised to 110 ° C., and the reaction is carried out for 30 hours. A solution containing the binder resin (b-3) represented by (binder resin solution (B-3): solid content concentration 40% by mass) was obtained. When the molecular weight of the obtained binder resin was measured in the same manner as in Synthesis Example 11, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 7700, and Mw / Mn was 2.21.

（上記式において、組成比は質量比である。）

(In the above formula, the composition ratio is the 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 propylene. 60 parts by mass of glycol monomethyl ether was charged, and 32 parts by mass of glycidyl methacrylate, 40 parts by mass of 3-methacryloxypropyltriethoxysilane, 11 parts by mass of benzyl methacrylate, 3 parts by mass of n-butyl methacrylate and 14 parts by mass of methacrylate were charged. After substituting with nitrogen in, the temperature of the solution was raised to 80 ° C. with gentle stirring. By holding at this temperature for 5 hours and polymerizing, a solution containing the binder resin (b-4) (hereinafter, binder resin solution (B-4) solid content concentration 35% by mass) was obtained. When the molecular weight of the obtained binder resin was measured in the same manner as in Synthesis Example 11, the weight average molecular weight (Mw) was 9500, the number average molecular weight (Mn) was 5800, and Mw / Mn was 1.64.

<Synthesis Example 15> Dispersant (d-2)
Using the method described in the 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, PME-200 (methoxypolyethylene glycol). Monomethacrylate and _{a polymer of a monomer represented by CH 2} = C (CH ₃ ) COO (C ₂ H ₄ O) _{n −} CH ₃ (n≈4)) 30 parts by mass were polymerized at once and randomly copolymerized. A reaction solution containing coalescence was obtained. Subsequently, the reaction solution was quenched with methanol, and the obtained reaction solution was washed with a 7% by mass aqueous sodium hydrogen carbonate solution and then with water. Then, the solvent was replaced with propylene glycol monomethyl ether acetate (PGMEA) to obtain a dispersant solution (D-2) containing the dispersant (d-2) in a yield of 80% by mass. The amine value of the obtained dispersant (d-2) was 160 mgKOH / g, Mw was 9500, Mw / Mn was 1.21, and the solid content of the dispersant solution (D-2) was 39.6% by mass. ..

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

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

[Preparation Example 3] Preparation of Dye Solutions (A-1) to (A-9) 5.00 parts by mass of the phthalocyanine compound (a-1) and 95.00 parts by mass of CPN as a solvent are weighed in a container and mixed with a stirrer. bottom. The obtained solution was pressure-filtered using a 0.2 μm polytetrafluoroethylene (PTFE) filter under a constant pressure condition of 0.05 MPa to obtain a dye solution (A-1). Further, each dye shown in Table 1 was prepared in the same manner as described above except that the phthalocyanine compounds (a-2) to (a-6), (a-8) and (a-9) were used as the phthalocyanine compounds, respectively. Solutions (A-2) to (A-6), (A-8) and (A-9) were obtained.
Regarding the dye solution (A-7), 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 were used as the solvent. Prepared in the same manner.

[Example 1]
20.00 parts by mass of the dispersion liquid (C-1), 23.15 parts by mass of the dye solution (A-1), 21.01 parts by mass of the binder resin solution (B-1), as a polymerizable compound of Nippon Kayakusha. "KAYARAD DPHA" (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 8.14 parts by mass, ADEKA's "NCI-930" (O-acyloxime compound) 1.53 parts by mass as a polymerization initiator , 0.05 parts by mass of Neos "FTX-218D" (fluorine-based surfactant) as a surfactant, 0.31 parts by mass of Showa Denko's "Karensu MT PE1" (polyfunctional thiol) as a reaction modifier, 0.10 parts by mass of BASF's "Irganox 1010" (phenolic antioxidant) as an antioxidant and 25.71 parts by mass of cyclopentanone (CNP) as a solvent were weighed into a container and mixed with a stirrer. The composition of Example 1 was obtained by pressure-filtering about 100 mL of this mixture using a 0.5 μm PTFE filter under a constant pressure condition of 0.05 MPa.

[Examples 2 to 13, Comparative Examples 1 to 3]
Table shows the types and blending amounts (parts by mass) of dispersions, dye solutions and binder resin solutions, and the blending amounts (parts by mass) of polymerizable compounds, polymerization initiators, surfactants, reaction modifiers, antioxidants and solvents. The compositions of Examples 2 to 13 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except as shown in 1. In Table 1, the types of [A] phthalocyanine compound, [B] binder resin, [C] infrared shielding agent, [D] dispersant and other pigments and the contents in the solid content of each of the obtained compositions are shown. Also shown. “CsWO” in Table 1 represents _{tungsten cesium oxide (Cs 0.33} WO _{3) obtained in Synthesis Example 10.}

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

Each composition was applied onto a glass substrate by a spin coating method so as to have a predetermined film thickness. Then, the coating film was heated at 100 ° C. for 120 seconds and exposed to ^{500 mJ / cm 2 with an i-line stepper.} Then, by heating at 220 ° C. for 300 seconds, an infrared shielding film having an average film thickness of 2.0 to 4.0 μm was produced on a glass substrate. Each average film thickness is shown in Table 1. The film thickness was measured with a stylus type step meter (“Alpha Step IQ” manufactured by Yamato Scientific Co., Ltd.). Next, the transmittance of the infrared shielding film produced on the glass substrate in each wavelength region was measured using a spectrophotometer (“V-7300” manufactured by JASCO Corporation) in comparison with the glass substrate. From the obtained spectrum, evaluation was performed according to the following evaluation criteria.

(Visible light transmission)
The average transmittance of 430-580 nm was calculated. If the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film decreases. In addition, the average transmittance was evaluated according to the following criteria.
A: 80% or more B: 70% or more and less than 80% C: less than 70%

(Visible transparent window range)
The range in which the transmittance in the range of 430 to 580 nm was 70% or more continuously was determined. When the range of 70% or more continuously is 175 nm or more, it is presumed to be highly practical because it has high sensitivity when used as an infrared shielding film. The visible and transparent window range was evaluated according to the following criteria.
A: 200 nm or more B: 175 nm or more and less than 200 nm C: less than 175 nm

(Infrared shielding range)
A range in which the transmittance in the range of 700 to 800 nm was continuously 20% or less was determined. When the range of 20% or less continuously is 20 nm or more, it is presumed to be highly practical because it has a high noise shielding function when used as an infrared shielding film. In addition, the infrared shielding range was evaluated according to the following criteria.
A: 30 nm or more B: 20 nm or more and less than 30 nm C: less than 20 nm

(Average Off-Slope)
In the range of 500-750 nm, the longest wavelength with a transmittance of 80% or more is (X), the shortest wavelength with a transmittance of 20% or less is (Y), and the average Off-Slope (Z) is as follows. Calculated by the formula. When the average Off-Slope is 0.45 or more, it is possible to improve the color reproducibility and noise shielding function of the obtained image when used as an infrared shielding film, and it is presumed to be highly practical. In addition, the average Off-Slope was evaluated according to the following criteria.
(Z) = 60 / ((Y)-(X))
AA: 0.60 or 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-resistant)
The infrared shielding film formed on the glass substrate is heated at 260 ° C. for 300 seconds using a hot plate, and the transmittance in each wavelength region before and after heating is measured by a spectrophotometer (“V-7300” by JASCO Corporation). Was measured in comparison with the glass substrate. At this time, the absorbance of the prepared infrared shielding film at the wavelength at which the transmittance is lowest in the range of 700 to 800 nm is (A1), the absorbance after heating at 260 ° C. at the same wavelength is (A2), and the absorbance retention rate = 100. The heat resistance at 260 ° C. was evaluated according to the following criteria as × (A1) / (A2). When the retention rate is 30% or more, when used as an infrared shielding film, it is possible to maintain high heat resistance by using it in combination with a protective film or the like, and it is presumed to be highly practical. In addition, the above retention rate was evaluated according to the following criteria.
AA: 90% or more A: 60% or more and less than 90% B: 30% or more and less than 60% C: less than 30%

(Defect suppression)
Each composition was applied onto a silicon substrate by a spin coating method, and the coating film was cured to form a cured film having a film thickness of about 1 μm. The defect density of the cured film was measured using a defect / foreign matter inspection device (“KLA 2351” manufactured by KLA-Tencor). It can be judged that the smaller the value of the defect density is, the higher the defect suppressing property is. The defect refers to a detection point having a size of 1 μm or more. Based on the above defect density, the defect suppression property was evaluated according to the following criteria.
A: 10 / cm ² or less B: 10 / cm ^{2 or} more 50 / cm ² or less C: 50 / cm ^{2 or} more

(PCD stability)
Each composition was applied onto a silicon substrate by a spin coating method to form a coating film having a film thickness of about 1 μm without curing the coating film. The defect density of the coating film was measured using a defect / foreign matter inspection device (“KLA 2351” manufactured by KLA-Tencor). Subsequently, the defect density of the coating film is measured at regular intervals, the time when the number of defects increases by 20% or more with respect to the initial value is measured, and the post-coating post-coating retention (PCD: Post) is performed according to the following criteria. Coating Delay) Stability was evaluated. It is presumed that the larger the value of PCD stability, the higher the practicality.
A: 24 hours or more B: 12 hours or more and less than 24 hours C: Less than 12 hours

As shown in Table 1 above, all of Examples 1 to 13 have visible light transmission, visible light transmission window range, infrared shielding range, average Off-Slope, heat resistance, defect suppression, and PCD stability. The evaluation was good. Among the examples using the phthalocyanine compound represented by the above formula (1), Examples 1 and 1 using the phthalocyanine compounds (a-1, a-3 to a-6) in which R has a substituent. It can be seen that 3 to 6 have higher heat resistance as compared with Example 2 using the phthalocyanine compound (a-2) in which R does not have a substituent. It can also be seen that, among the above-mentioned examples using the phthalocyanine compound in which R has a substituent, Examples 1, 3 and 4 also have good visible light transmission.

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

Claims (9)

A composition for an optical sensor containing a phthalocyanine compound represented by the following formula (1) and a binder resin.

(In the formula (1), each of the plurality of Rs is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group. The plurality of Xs are independent of each other. A plurality of Xs may be bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. M is two hydrogen atoms and divalent. It is a metal atom or a derivative of a trivalent or tetravalent metal atom. A plurality of ns are independently integers of 3 to 6). The composition for an optical sensor according to claim 1, wherein the plurality of Rs are independently an alkyl group having a substituent or an aryl group having a substituent. The composition for an optical sensor according to claim 1 or 2, wherein the binder resin has an oxylanyl group, an oxetanyl group, a (meth) acryloyl group, an alkoxysilyl group, or a combination thereof. The composition for an optical sensor according to any one of claims 1 to 3, wherein the binder resin has a ring structure in the main chain. A composition for an optical sensor containing a phthalocyanine compound represented by the following formula (2).

(In the formula (2), a plurality of Rs are independently alkyl groups having a substituent or an aryl group having a substituent. A plurality of Xs are independently hydrogen atoms, halogen atoms or or. It is an alkyl group. A plurality of Xs may be bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. M is a two hydrogen atom, a divalent metal atom, or a trivalent or tetravalent group. It is a derivative of the metal atom of. A plurality of n are independently integers of 3 to 6). The composition for an optical sensor according to any one of claims 1 to 5, wherein the substituents of the alkyl group and the aryl group represented by the plurality of Rs are heteroatoms. The composition for an 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. The composition for an optical sensor according to any one of claims 1 to 7, further comprising a metal oxide, a copper compound (excluding the above-mentioned phthalocyanine compound), or an infrared shielding agent which is a combination thereof. The composition for an optical sensor according to claim 8, wherein the metal oxide is tungsten cesium oxide.