KR20210071971A - Compositions for optical sensors - Google Patents

Abstract

A composition for an optical sensor capable of forming an optical filter for an optical sensor having good properties regarding visible light transmittance and infrared shielding property is provided. This invention is a composition for optical sensors containing the phthalocyanine compound represented by following formula (1), and binder resin. In Formula (1), some R is each independently an alkyl group which has a substituent or unsubstituted, or an aryl group which has a substituent or unsubstituted. A plurality of X's are each independently a hydrogen atom, a halogen atom, or an alkyl group. A 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. A plurality of n is each independently an integer of 3-6.

Description

Compositions for optical sensors

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

BACKGROUND ART A video camera, a digital camera, a mobile phone with a camera function, or the like is equipped with a solid-state image sensor that is an optical sensor. As a solid-state image sensor, a CCD (Charge-Coupled Device) image sensor, a CMOS (Complementary MOS) image sensor, etc. are specifically known. The sensitivity of the photodiode provided in these solid-state imaging elements ranges from a visible region to an infrared region. For this reason, in a solid-state image sensor, the filter for interrupting|blocking infrared rays is formed. By this optical filter (infrared cut filter), the sensitivity of a solid-state image sensor can be corrected so that it may approximate human visibility. Also in optical sensors other than a solid-state image sensor, the filter for blocking infrared rays may be formed similarly.

The optical filter contains a dye and a pigment as an infrared shielding agent. The infrared shielding agent is required to have a characteristic of absorbing infrared rays while sufficiently transmitting visible light. As one of these infrared shielding agents, the use of a phthalocyanine compound as a good shielding agent of especially near infrared rays is examined (refer Unexamined-Japanese-Patent No. 2008-201952).

Japanese Laid-Open Patent Publication No. 2008-201952

However, in the conventional optical filter using a phthalocyanine compound, defects, such as a foreign material, may arise because of influences, such as compatibility. Such a defect may affect the visible light transmittance, infrared shielding property, etc. of an optical filter. In addition, when forming the infrared shielding film of the optical filter by coating of a composition containing a dye such as a phthalocyanine compound, if the leaving time after coating is long, defects such as foreign matter are likely to occur in the obtained infrared shielding film. In a production process, it is desired that an infrared shielding film with few defects such as foreign matter be obtained even if cured after being left for a while after coating.

Moreover, in the conventional optical filter, it is not fully satisfied also about visible light transmittance and infrared rays shielding property. Specifically, when an optical filter is used as an infrared cut filter of an optical sensor such as a solid-state image sensor, the visible light transmittance is high and the infrared transmittance is not only high, but also a wavelength region in which the visible light transmittance is high, or a wavelength in which the infrared transmittance is low. It is calculated|required that the area|region is wide, or that the wavelength range with high visible light transmittance and the wavelength range with low infrared transmittance are close. 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 on the basis of the above circumstances, and an object thereof is for an optical sensor capable of forming an optical filter for an optical sensor having few defects such as foreign matter and good properties regarding visible light transmittance and infrared shielding properties. to provide a composition.

The invention made in order to solve the said subject is the composition for optical sensors containing the phthalocyanine compound represented by following formula (1), and binder resin.

(In formula (1), a plurality of R's are each independently a substituent or unsubstituted alkyl group, or a substituent or unsubstituted aryl group. A plurality of X's are each independently a hydrogen atom, a halogen atom, or A plurality of X 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. A plurality of n is each independently an integer of 3 to 6.)

Another invention made in order to solve the said subject is the composition for optical sensors containing the phthalocyanine compound represented by following formula (2).

(In formula (2), a plurality of R's are each independently an alkyl group having a substituent or an aryl group having a substituent. A plurality of X's are each independently a hydrogen atom, a halogen atom, or an alkyl group. 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. A plurality of n is each Independently, it is an integer from 3 to 6.)

ADVANTAGE OF THE INVENTION According to this invention, there are few defects, such as a foreign material, and it can provide the composition for optical sensors which can form the optical filter for optical sensors which has favorable characteristics regarding visible light transmittance and infrared-shielding property.

(Form for implementing the invention)

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

<Composition (I) for optical sensor>

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

([A1] phthalocyanine compound)

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

In Formula (1), some R is each independently an alkyl group which has a substituent or unsubstituted, or an aryl group which has a substituent or unsubstituted. A plurality of X's are each independently a hydrogen atom, a halogen atom, or an alkyl group. A 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. A plurality of n is each independently an integer of 3-6.

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, and a t-butyl group having 1 to 30 carbon atoms. and a chain or branched alkyl group. As an upper limit of carbon number of this alkyl group, 12 is preferable, 8 is more preferable, and 4 is still more preferable.

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

As said R, it is preferable from points, such as heat resistance of the optical filter obtained, that it is a substituent which has a substituent or an unsubstituted aryl group.

Although the alkyl group and the aryl group respectively represented by said some R may have a substituent, it is not necessary to have it, but it is preferable to have a substituent. That is, it is preferable that said some R is each independently an alkyl group which has a substituent, or an aryl group which has a substituent. In this way, when the plurality of R has a substituent, the compatibility of the [A1] phthalocyanine compound is higher, defects such as foreign matter in the obtained optical filter are more suppressed, and the properties related to visible light transmittance and infrared shielding property are also better do. Moreover, the heat resistance of the optical filter obtained also improves when said some R has a substituent.

As a substituent which the alkyl group and aryl group respectively represented by said some R may have, hydrocarbon groups, such as an alkenyl group and an alkynyl group, may be sufficient, but a group which has a hetero atom is preferable. A hetero atom means atoms other than a hydrogen atom and a carbon atom. When the alkyl group and the aryl group respectively represented by the plurality of R have a substituent having a hetero atom, compatibility, etc. is higher, and defects such as foreign matter in the obtained optical filter are more suppressed, and properties related to visible light transmittance and infrared shielding properties becomes better. Moreover, the heat resistance of the optical filter obtained also improves when said some R has a substituent which has a hetero atom. As said 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.

As a substituent which has a hetero atom, a halogen atom, an alkoxy group, an alkylthio group, a cyano group, a nitro group, a carboxy group, a hydroxyl group, a thiol group, an amino group, etc. are mentioned.

A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom, A fluorine atom is preferable.

As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, A methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

Examples of the alkylthio group include a methylthio group (CH ₃ -S-), an ethylthio group (C ₂ H ₅ -S-), and a propylthio group (C ₃ H ₇ -S-), and a methylthio group and an 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. Moreover, it is also preferable that they are a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, or a combination thereof.

Although said some R may be same or different, it is preferable that it is 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 bonded to each other. Usually, two Xs couple|bonded with the same benzene ring among several X couple|bond with each other, and form an aromatic ring together with the carbon chain to which these couple|bonded. As an aromatic ring formed, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. The hydrogen atoms of these aromatic rings may be substituted with a hydrocarbon group or another substituent.

As said X, a hydrogen atom is preferable. In addition, although some X may be same or different, the same thing is preferable.

Examples of the divalent metal atom represented by M include Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, Pb, and the like. In addition, a divalent metal atom means the metal atom which can become a divalent cation.

Here, the derivative of a metal atom means the group of atoms containing a metal atom. A trivalent metal atom means a metal atom which can become a trivalent cation. Al, In, etc. are mentioned as a trivalent metal atom. A tetravalent metal atom means a metal atom which can become a tetravalent cation. As a tetravalent metal atom, Si, Ge, Sn, etc. are mentioned. In addition, a semimetal atom is also contained in a metal atom. Examples of derivatives of 3 or tetravalent metal atom represented by the above M, 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.

As said 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 a lower limit of said n, 4 is preferable. As an upper limit of said n, 5 is preferable and 4 is more preferable. Although a plurality of n may be the same or different, the same thing is preferable.

[A1] 680 nm is preferable, as for the minimum of the maximum absorption wavelength of a phthalocyanine compound, 700 nm is more preferable, 720 nm is still more preferable. On the other hand, 1,000 nm is preferable, as for the upper limit of this maximal absorption wavelength, 900 nm is more preferable, 800 nm is more preferable, and 750 nm is still more preferable. [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 properties regarding visible light transmittance and infrared shielding properties.

[A1] The method for synthesizing the phthalocyanine compound is not particularly limited, and it can be synthesized by combining known methods. For example, it can synthesize|combine by making a metal or a metal derivative react with the 1, 3- diiminoisoindoline type compound represented by the phthalonitrile type compound represented by following formula (i) or Formula (ii).

In formulas (i) and (ii), R, X and n have the same meaning as in formula (1).

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

Reaction temperature is 60-300 degreeC, for example, Preferably it is 100-220 degreeC. 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 a solvent used for reaction, an organic solvent with a boiling point of 60 degreeC or more is preferable, and 80 degreeC or more organic solvent is more preferable.

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

The reaction is carried out in the presence or absence of a catalyst, but the presence of a catalyst is preferable. Examples of the catalyst include inorganic catalysts such as ammonium molybdate, DBU (1,8-diazabicyclo[5.4.0]undeca-7-ene), DBN (1,5-diazabicyclo[4.3.0]nona- A basic organic catalyst such as 5-ene) can be used.

When M in Formula (1) is a phthalocyanine compound of two hydrogen atoms, the 1,3-diiminoisoindoline compound represented by the phthalonitrile-type compound represented by Formula (i) or Formula (ii), and a metal It can be prepared by reacting sodium or potassium metal under the above reaction conditions, and then treating sodium or potassium as a central metal with hydrochloric acid, sulfuric acid, or the like to desorb.

After completion of the reaction, the phthalocyanine compound represented by Formula (1) can be obtained by distilling off the solvent or discharging the reaction solution as a poor solvent for the phthalocyanine compound to precipitate the target substance and filtering the precipitate. If necessary, by further purifying by a known purification method such as recrystallization or column chromatography, a higher purity target product can be obtained.

In addition, the phthalonitrile-type compound represented by Formula (i), and the 1, 3- diiminoisoindoline type compound represented by Formula (ii) can be synthesize|combined with reference to a well-known method. For example, it can synthesize|combine with reference to the method described in Unexamined-Japanese-Patent No. 2003-516421.

As the lower limit of the content of the [A1] phthalocyanine compound to the total solid content (all components other than the solvent) in the composition (I), 0.1 mass % is preferable, 0.5 mass % is more preferable, and 1 mass % is further It is preferable, and 2 mass % is still more preferable. On the other hand, as an upper limit of this content, 30 mass % is preferable, 15 mass % is more preferable, 10 mass % is still more preferable, 8 mass % is still more preferable. [A1] By making content of a phthalocyanine compound into the said range, the characteristic regarding the visible light transmittance and infrared-shielding property of the optical filter obtained becomes more favorable.

[A1] A phthalocyanine compound may be used individually by 1 type, and may be used in mixture of 2 or more types.

([B] binder resin)

[B] Binder resin is a component used as a matrix by preserving the [A1] phthalocyanine compound or the like in the obtained optical filter.

[B] In order to improve strength, sensitivity, heat resistance, etc., it is preferable to have a polymeric group, and, as for binder resin, it is more preferable to have a structural unit containing a polymeric group. Examples of the polymerizable group include an oxiranyl group, an oxetanyl group, a (meth)acryloyl group, a vinyl group, and an alkoxysilyl group, and an oxiranyl group, an oxetanyl group, a (meth)acryloyl group, an alkoxysilyl group, or These combinations are preferable, and a (meth)acryloyl group is more preferable.

As a monomer which provides the structural unit containing a polymeric group, (meth)acrylic-acid glycidyl, 3-(meth)acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth)acryl rate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate, 3-methacryloxypropyltriethoxysilane, etc. are mentioned.

Also, for example, by reacting a resin having a structural unit having a carboxy group with a group that reacts with a carboxy group (oxiranyl group, oxetanyl group, etc.) and a compound having a polymerizable group such as a (meth)acryloyl group , a structural unit containing a polymerizable group may be introduced.

As a lower limit of content of the structural unit which has a polymeric group in [B] binder resin, 5 mass % is preferable with respect to 100 mass % of [B] binder resin, 10 mass % is more preferable, 15 mass % is More preferably, 30 mass %, 50 mass %, or 75 mass % may be still more preferable. On the other hand, as an upper limit of this content, 95 mass % is preferable, 90 mass % is more preferable, 85 mass % is still more preferable.

[B] It is preferable that binder resin has a ring structure in a principal chain for heat resistance improvement. As reduced water of this ring structure, although 3-12 may be sufficient, for example, 5-8 are preferable.

As a monomer which provides the structural unit containing a ring structure to a main chain, an N-substituted maleimide-type monomer, a cycloolefin, etc. are mentioned.

An N-substituted maleimide-type monomer is a compound in which the hydrogen atom couple|bonded with the nitrogen atom in maleimide was substituted by the substituent. As said substituent, a hydrocarbon group is preferable, the hydrocarbon group which has 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, and dicyclopentadiene-based olefins.

In addition, a phenol resin etc. can also be used as binder resin which has a ring structure in a principal chain.

As content of the structural unit which contains a ring structure in the main chain in [B] binder resin, Preferably it is 1 mass % - 50 mass % with respect to 100 mass % of [B] binder resin, More preferably, 5 mass % -30 mass %.

[B] It is preferable that an acidic group is contained in binder resin. As an acidic group, a carboxy group, an acid anhydride group, phenolic hydroxyl group, a sulfo group etc. are mentioned, for example. Among the above, as an acidic group, a carboxy group is preferable. [B] It is preferable that binder resin is resin containing the structural unit which has one or more acidic groups. [B] When binder resin has an acidic group, favorable alkali solubility can be shown. [B] When the binder resin has alkali solubility, alkali development is enabled and an optical filter having a desired pattern shape can be formed.

As a monomer which provides the structural unit containing an acidic group, As a monomer which has a carboxy group, For example, Unsaturated monocarboxylic acid like (meth)acrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or anhydrides thereof; Mono [(meth) acryloyloxyalkyl] ester of polyvalent carbonic acid having a divalent or higher value, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate.

As a monomer which has a phenolic hydroxyl group, 4-vinyl phenol, 4-isopropenyl phenol, 4-hydroxyphenyl (meth)acrylate, etc. are mentioned.

[B] As content of the structural unit containing an acidic group in binder resin, with respect to 100 mass % of [B] binder resin, Preferably it is 1 mass % - 50 mass %, More preferably, 5 mass % - 30 mass %to be.

[B] The binder resin may further contain other structural units. As a monomer which provides another structural unit, for example,

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 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, poly Propylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acryl rate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumyl phenol, glycidyl (meth) Acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane (meth)acrylic acid esters such as

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, etc. of vinyl ether,

The macromonomer etc. which have a mono(meth)acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, and polysiloxane, are mentioned.

[B] Binder resin can be obtained by superposing|polymerizing by a well-known method using each monomer etc. mentioned above. In addition, [B] binder resin may be used individually by 1 type, or may use 2 or more types.

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

As a lower limit of content of binder resin [B] which occupies for the total solid in the said composition (I), 5 mass % is preferable, 10 mass % is more preferable, 20 mass % is still more preferable. On the other hand, as an upper limit of this content, 70 mass % is preferable, 60 mass % is more preferable, and 50 mass % is still more preferable. [B] By making content of binder resin into the said range, heat resistance etc. can also be improved, fully exhibiting the characteristic regarding the visible light transmittance and infrared-shielding property of the optical filter obtained.

([C] Infrared shielding agent)

[C] The infrared shielding agent is a metal oxide, a copper compound (excluding the [A1] phthalocyanine compound), or a combination thereof. [C] As an infrared shielding agent, the compound which has a maximum absorption wavelength in the range of 800 nm or more and 2000 nm or less is preferable. By using this [C] infrared shielding agent together with the [A1] phthalocyanine compound, the infrared shielding performance of the optical filter obtained improves more.

[C] As the metal oxide as the infrared shielding agent, for example, a tungsten oxide-based compound, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO _{2 )} ), spinel (MgAl ₂ O ₄ ), and the like.

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

[C] As the infrared shielding agent, a metal oxide is preferable, and a tungsten oxide-based compound is more preferable. The tungsten oxide-based compound is an infrared shielding agent having high absorption (ie, high infrared shielding properties) for infrared rays (especially infrared rays having a wavelength of about 800 nm or more and 1200 nm or less) and low absorption for visible light. Therefore, when the said composition (I) contains a tungsten oxide type compound, infrared-shielding property can be improved, maintaining favorable visible light transmittance of the optical filter obtained. [C] An infrared shielding agent may be used individually by 1 type, and may be used in mixture of 2 or more type.

As a tungsten oxide type compound, it is more preferable that it is a tungsten oxide type compound represented by following formula (3).

A _x WO _y … (3)

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

Examples of the metal element represented by A in the formula (3) include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn. , Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like. The number of metal elements represented by A may be 1 type, or 2 or more types may be sufficient as them.

As said A, an alkali metal is preferable, Rb and Cs are more preferable, and Cs is still more preferable. 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. 0.01 is preferable and, as for the minimum of x, 0.1 is more preferable. On the other hand, when x is 1.1 or less, generation of an impurity phase in the tungsten oxide-based compound can be more reliably avoided. 1 is preferable and, as for the upper limit of x, 0.5 is more preferable.

When y in said Formula (3) is 2.2 or more, the chemical stability as a material can be improved more. As for the lower limit of y, 2.5 is preferable. 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 formula (3) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ , and the like, and Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . preferred, more preferably _{Cs 0.33} WO _{3 .}

[C] The infrared shielding agent is preferably fine particles. [C] As an upper limit of the average particle diameter (D50) of an infrared shielding agent, 500 nm is preferable, 200 nm is more preferable, 50 nm is still more preferable, and 30 nm is still more preferable. When an average particle diameter is below the said upper limit, visible light transmittance can be improved more. On the other hand, from reasons such as ease of handling during production, the average particle diameter of the [C] infrared shielding agent is usually 1 nm or more, and may be 10 nm or more.

[C] Although an infrared shielding agent can also be synthesize|combined by a well-known method, it is available as a commercial item. When the metal oxide is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by, for example, heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. Moreover, a tungsten oxide type compound can be obtained also as a dispersion of tungsten microparticles|fine-particles, such as "YMF-02" by Sumitomo Kinzoku Kosan, for example.

The lower limit of the content of the [C] infrared shielding agent to the total solid content in the composition (I) is preferably 1 mass %, more preferably 5 mass %, still more preferably 10 mass %, and 15 mass % more preferably. On the other hand, as an upper limit of this content, 70 mass % is preferable, 50 mass % is more preferable, 40 mass % is still more preferable, 30 mass % is still more preferable. [C] By making content of an infrared ray shielding agent into the said range, the characteristic regarding visible light transmittance and infrared ray shielding property of the optical filter obtained becomes more favorable.

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 an upper limit of this mass ratio ([C]/[A1]), 40 is preferable, 20 is more preferable, and 10 is still more preferable. When the content ratio of the [A1] phthalocyanine compound and the [C] infrared shielding agent is within the above range, the properties regarding visible light transmittance and infrared shielding properties of the obtained optical filter become more favorable.

([D] dispersant)

It is preferable that the said composition (I) further contains [D] a dispersing agent. The [D] dispersing agent improves the uniform dispersibility of the [C] infrared shielding agent (especially a metal oxide), and the properties regarding visible light transmittance and infrared shielding properties of the obtained optical filter become more favorable.

[D] Examples of the dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, a polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, and a polyester. A system dispersing agent, a (meth)acrylic type dispersing agent, etc. are mentioned. Among these, a (meth)acrylic-type dispersing agent is preferable. [D] It is preferable that a dispersing agent is a block copolymer.

[D] The dispersant is commercially available, for example, as a (meth)acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK) manufacture), as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above, manufactured by BYK), Solsperse 76500 ( Lubrizol Co., Ltd.), as a polyethyleneimine dispersing agent, Solsperse 24000 (Lubrizol Co., Ltd.), as a polyester dispersing agent, Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), etc., BYK-LPN21324 (made by BYK) etc. are mentioned.

[D] As a lower limit of the amine titer of a dispersing agent, 10 mgKOH/g is preferable, 40 mgKOH/g is more preferable, 80 mgKOH/g is still more preferable. On the other hand, as an upper limit of this amine titer, 300 mgKOH/g is preferable, 200 mgKOH/g is more preferable, 160 mgKOH/g is still more preferable. By using the dispersing agent which has such an amine value, the dispersibility of the [C] infrared shielding agent improves, and the characteristic of the optical filter obtained can be improved more. In addition, "amine number" is the number of mg of HCl and equivalent KOH required to neutralize 1 g of solid content of a dispersing agent.

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

([E] polymerizable compound)

It is preferable that the said composition (I) further contains the [E] polymeric compound. When the said composition (I) contains the [E] polymeric compound, favorable hardenability, favorable heat resistance of the optical filter obtained, etc. can be exhibited. [E] The polymerizable compound refers to a compound having two or more polymerizable groups. In addition, the [B] binder resin which has two or more polymerizable groups is not contained in the [E] polymerizable compound. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. [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 a compound having two or more (meth)acryloyl groups is preferred. more preferably. [E] A polymeric compound can be used 1 type or in mixture of 2 or more types.

Examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylate, which is a reaction product of an aliphatic polyhydroxy compound and (meth)acrylic acid, 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, and a reaction product of (meth)acrylate having a hydroxyl group and an acid anhydride The polyfunctional (meth)acrylate etc. which have a carboxyl group which are etc. are mentioned.

Here, as said aliphatic polyhydroxy compound, For example, divalent aliphatic polyhydroxy compounds, such as ethylene glycol, propylene glycol, polyethyleneglycol, polypropylene glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythryl and trivalent or higher aliphatic polyhydroxy compounds such as ritol. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta. (meth)acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate etc. are mentioned, for example. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid 2 and tetrabasic acid dianhydrides such as anhydride and benzophenone tetracarboxylic dianhydride.

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-hexanedioldi(meth) Acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol Fluorenedi (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2-(2'-vinyloxyethoxy) ) Ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, urethane (meth)acrylic a rate compound etc. are mentioned.

Among the compounds which have 2 or more (meth)acryloyl groups, polyfunctional (meth)acrylate is preferable, and polyfunctional (meth)acrylate which has 3 or more and 10 or less (meth)acryloyl groups is more preferable. Do. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.

As a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, and a urea structure are mentioned, for example. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra( Alkoxymethyl) benzoguanamine, N,N,N',N'- tetra(alkoxymethyl) glycoluril, etc. are mentioned.

As a lower limit of content of [E] polymeric compound which occupies for the total solid in the said composition (I), 5 mass % is preferable, 10 mass % is more preferable, 20 mass % is still more preferable. On the other hand, as an upper limit of this content, 60 mass % is preferable, 50 mass % is more preferable, and 40 % is still more preferable.

([F] polymerization initiator)

The composition (I) preferably contains [F] a polymerization initiator. [F] Although a photoinitiator, a thermal polymerization initiator, etc. are mentioned as a polymerization initiator, A photoinitiator is preferable. Thereby, photosensitivity (radiation sensitivity) can be provided to the said composition (I). The photopolymerization initiator refers to a compound that generates active species capable of initiating polymerization such as [E] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. [F] A polymerization initiator can be used 1 type or in mixture of 2 or more types.

[F] As the polymerization initiator, for example, a thioxanthone-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an O-acyloxime-based compound, an onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds, and the like are mentioned. Among these, a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound are preferable, and an O-acyl oxime type compound is more preferable.

As the thioxanthone-based compound, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 and 4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropyl thioxanthone.

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

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2). ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

Moreover, when using a biimidazole type compound, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The "hydrogen donor" here means a compound which can donate a hydrogen atom with respect to the radical which generate|occur|produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzooxazole; and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of Japanese Patent Application Laid-Open No. 57-6096 and Japanese Unexamined Patent Publication No. 2003-238898.

Examples of the O-acyloxime compound include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-a2-methyl-4-(2,2-dimethyl-1,3-) dioxolanyl) methoxybenzoyl ｝-9H-carbazol-3-yl]-1-(O-acetyloxime); and the like. As a commercial item of an O-acyl oxime type compound, NCI-831, NCI-930 (above, ADEKA Corporation make), OXE-03, OXE-04 (above, BASF company make), etc. can also be used.

When using a photoinitiator, a sensitizer can also be used together. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. , 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl ) coumarin, 4-(diethylamino)chalcone, etc. are mentioned.

As a minimum of content of the [F] polymerization initiator which occupies for the total solid in the said composition (I), 1 mass % is preferable and 3 mass % is more preferable. On the other hand, as an upper limit of this content, 30 mass % is preferable and 10 mass % is more preferable.

(Other organic dyes)

The composition (I) may contain a known organic dye other than the organic dye as the [A1] phthalocyanine compound and [C] the copper compound as an infrared shielding agent. Examples of other organic dyes include a diminium compound, a squarylium compound, a cyanine compound, a naphthalocyanine compound, a quaterrylene compound, an aminium compound, an iminium compound, an azo compound, an anthraquinone compound, a porphyrin compound, a pyrrolopyrrole compound, an oxonol compound, a croconium compound, a hexapyrine compound, and the like (except those containing a copper atom). Moreover, phthalocyanine compounds other than the [A1] phthalocyanine compound and the [C] phthalocyanine compound as an infrared shielding agent can also be used.

Moreover, it is preferable to use together the [A1] phthalocyanine compound and phthalocyanine compounds other than the [A1] phthalocyanine compound (hereinafter also referred to as "a [a] phthalocyanine compound"). [a] As a lower limit of the maximum absorption wavelength of a phthalocyanine compound, 600 nm is preferable and 650 nm is more preferable. On the other hand, as an upper limit of the maximum absorption wavelength of [a] phthalocyanine compound, 900 nm is preferable, 850 nm is more preferable, 800 nm is more preferable in some cases, and 750 nm is still more preferable in some cases. 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, as an upper limit of this difference, 100 nm is preferable, 80 nm is more preferable, and 60 nm is still more preferable. [a] As for the phthalocyanine compound, a conventionally well-known various phthalocyanine compound is mentioned.

As a lower limit of content of the [A1] phthalocyanine compound which occupies for all the organic dyes in the said composition (I), 50 mass % is preferable, 70 mass % is more preferable, 80 mass % may be more preferable, 90 Mass % may be more preferable, and 99 mass % may be more preferable. As an organic dye, it may be preferable to contain substantially only the [A1] phthalocyanine compound. The said composition (I) can raise productivity by reducing content of another organic dye in this way.

(additive)

The said composition (I) may contain various additives as needed other than the above-mentioned [A1]-[F] components and other organic dyes.

As an additive, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, aggregation inhibitor, a residue improving agent, developability improving agent, a reaction modifier etc. are mentioned, for example.

As surfactant, a fluorosurfactant, silicone surfactant, etc. are mentioned.

As the adhesion promoter, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrime Toxysilane etc. are mentioned.

As antioxidant, 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. As content of antioxidant, it can be normally set as 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] phthalocyanine compounds.

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

As an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

As the residue improving agent, 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 and ,2-propanediol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol.

As a developability improving agent, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned can

Polyfunctional thiol etc. are mentioned as a reaction modifier.

As a lower limit of content of components other than the above-mentioned [A1]-[F] components and other organic dyes occupied in the total solid content in the said composition (I), 0.1 mass % is preferable, and 1 mass % is more preferable. Do. On the other hand, as an upper limit of this content, 10 mass % is preferable and 5 mass % is more preferable.

(menstruum)

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

As such a solvent, for example,

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 monomethyl ether (poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

lactic acid alkyl esters such as methyl lactate and ethyl lactate;

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

Keto alcohols such as diacetone alcohol;

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 (poly)alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;

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

chain ketones such as methyl ethyl ketone, 2-heptanone and 3-heptanone; ketones such as cyclic ketones such as cyclopentanone and cyclohexanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylic acids, such as 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyethyl acetate, 3-methyl-3-methoxybutylpropionate esters,

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate , other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene;

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

and the like.

Content of the solvent in the said composition (I) is not specifically limited. As a lower limit of the solid content concentration (total concentration of each component excluding a solvent) in the said composition (I), 5 mass % is preferable and 10 mass % is more preferable. On the other hand, as an upper limit of this solid content concentration, 50 mass % is preferable and 40 mass % is more preferable. By making solid content concentration into the said range, dispersibility, stability, applicability|paintability, etc. become more favorable.

(Preparation method)

It does not specifically limit as a manufacturing method of the said composition (I), It can prepare by mixing each component. For example, when the composition contains [C] a metal oxide as an infrared shielding agent and [D] a dispersing agent, first prepare a dispersion containing [C] an infrared shielding agent, [D] a dispersing agent, and a solvent, A method of adding and mixing the [A1] phthalocyanine compound, [B] binder resin, and other components as necessary to this dispersion liquid can be adopted. The dispersion or the composition (I) may be subjected to filtration if necessary to remove aggregates.

<Composition for optical sensor (II)>

Composition (II) for an optical sensor according to an embodiment of the present invention (hereinafter also simply referred to as “composition (II)”) contains [A2] a phthalocyanine compound. [A2] A phthalocyanine compound is a compound represented by 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 matter and having favorable properties regarding visible light transmittance and infrared shielding properties.

In Formula (2), some R is each independently an alkyl group which has a substituent, or an aryl group which has a substituent. A plurality of X's are each independently a hydrogen atom, a halogen atom, or an alkyl group. A 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. A plurality of n is each independently an integer of 3-6.

The [A2] phthalocyanine compound is the same as the [A1] phthalocyanine compound described above, except that the plural Rs are each independently an alkyl group having a substituent or an aryl group having a substituent. [A2] The preferable aspect of the phthalocyanine compound is also the same as that of the above-mentioned [A1] phthalocyanine compound.

The composition (II) is the same as the composition (I) described above, except that the [A2] phthalocyanine compound is contained in place of the [A1] phthalocyanine compound, and the [B] binder resin is not an essential component. It is preferable that the said composition (II) contains binder resin [B]. In addition, the specific form and suitable form of the said composition (II) are the same as that of the above-mentioned composition (I).

<Infrared shielding film>

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 simply referred to as “composition”), an infrared shielding film for an optical filter can be formed. can This infrared shielding film has few defects, such as a foreign material, and has favorable characteristics regarding visible light transmittance and infrared rays shielding property.

The said infrared shielding film can be formed with the following method, for example. First, after apply|coating the said composition on a support body, prebaking is performed, a solvent is evaporated and a coating film is formed. Next, after exposing this coating film, it develops using a developing solution, and melt|dissolves and removes the unexposed part of the coating film. Thereafter, by post-baking, the infrared shielding film (I) patterned into a predetermined shape is obtained. In addition, when the said composition does not contain the [E] polymeric compound and the [F] polymerization initiator, it is not necessary to perform hardening processing, such as exposure. In addition, it is not necessary to perform a development process, and in this case, an unpatterned infrared-shielding film can be formed.

As said support body to which the said composition is apply|coated, a transparent substrate, a microlens, a color filter, etc. correspond. Appropriate coating methods, such as the spray method, the roll coating method, the spin coating method (spin coating method), the slit die coating method (slit coating method), and the bar coating method, can be employ|adopted for the said application|coating method.

As conditions of heat drying in the said prebaking, they are 70 degreeC or more and 110 degrees C or less, 1 minute or more and 10 minutes or less grade, for example.

As a light source of the radiation used for exposure of a coating film, For example, a lamp light source, such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, argon ion laser, YAG laser, XeCl Laser light sources, such as an excimer laser and a nitrogen laser, etc. are mentioned. As the exposure light source, an ultraviolet LED may be used. As for a wavelength, the radiation which exists in the range of 190 nm or more and 450 nm or less is preferable. The radiation dose is generally about 10 J/m 2 or more and 50,000 J/m 2 or less.

As said developing solution, an alkali developing solution is common. Examples of the alkaline developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5 Aqueous solutions, such as -diazabicyclo-[4.3.0]-5-nonene, are preferable. 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, for example. In addition, after image development, it washes with water normally.

As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (drilling) developing method, etc. are applicable. The developing conditions are about 5 seconds or more and 300 seconds or less at normal temperature.

As conditions for post-baking, they are 180 degreeC or more and 280 degrees C or less normally, 1 minute or more and 60 minutes or less grade.

As a lower limit of the average film thickness of the infrared shielding film formed in this way, it is 0.5 micrometer normally, and 1 micrometer is preferable. On the other hand, as an upper limit of this average film thickness, it is 10 micrometers normally, and 5 micrometers is preferable. When the average film thickness of infrared shielding is the said range, the balance of visible light transmittance and infrared rays shielding property becomes a more favorable thing.

<Optical filter>

The infrared shielding film formed of the composition according to an embodiment of the present invention can be used for an optical filter. The optical filter having the infrared shielding film has few defects such as foreign matter and has good properties regarding visible light transmittance and infrared shielding properties. The said optical filter is used as an optical filter of optical sensors, such as a solid-state image sensor.

The said optical filter may consist only of the said infrared-shielding film, and what consists of a structural member different from the said infrared-shielding film may be sufficient as it. For example, the said optical filter may be a laminated body which has a layer different from the said infrared-shielding film.

It is preferable that the said infrared ray shielding film is incorporated in optical sensors, such as a solid-state image sensor, as one structural member. In this case, the said infrared shielding film functions as an optical filter (infrared cut filter) by itself. By incorporating the infrared shielding film into the optical sensor, it is possible and preferable to obtain a large process margin. When the infrared shielding film is incorporated into the solid-state imaging element, the infrared shielding film is disposed, for example, on the outer surface side of the microlens of the solid-state imaging element, between the microlens and the color filter, between the color filter and the photodiode, etc. can do. It is preferable that the said infrared-shielding film is laminated|stacked between a microlens and a color filter, or between a color filter and a photodiode.

The optical filter may be one in which the infrared shielding film is laminated on the surface of a transparent substrate. Glass, transparent resin, etc. are employ|adopted as said transparent substrate. 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 etc. in a solid-state image sensor.

The optical sensor, such as a solid-state image sensor provided with the optical filter, is useful for a digital camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, an automobile camera, a portable information terminal, a PC, a video game, a medical device, etc. Do.

<Optical sensor>

The said optical filter is used for optical sensors, such as a solid-state image sensor. Since the optical filter has few defects such as foreign matter and has good properties regarding visible light transmittance and infrared shielding properties, an optical sensor such as a solid-state image pickup device having the optical filter has high sensitivity, color reproducibility, etc., and is excellent in practicality .

Hereinafter, a solid-state image sensor will be described as an example of the optical sensor. The solid-state imaging device generally has a structure in which a layer in which a plurality of photodiodes are disposed, a color filter, and a microlens are stacked in this order. In addition, a planarization layer may be formed between these layers. In the said solid-state image sensor, light enters from the microlens side. Incident light passes through the microlens and the color filter, and reaches the photodiode. In addition, about the color filter, in each of the filters of R (red), G (green), and B (blue), for example, it is comprised so that only the light of a specific wavelength range transmits.

In the solid-state imaging device, the optical filter (infrared shielding film) is disposed on the outer surface side of the microlens, between the microlens and the color filter, and between the color filter and the layer on which the plurality of photodiodes are disposed. may be formed. It is preferable that the said optical filter is laminated|stacked between a microlens and a color filter, or between a color filter and a photodiode. In addition, between the said optical filter and a microlens, a color filter, a photodiode, etc., another layer (planarization layer etc.) may be further formed.

As a specific example of the said solid-state image sensor, CCD, CMOS, etc. as a camera module are mentioned. The solid-state imaging device is useful for digital cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, portable information terminals, personal computers, video games, medical devices, and the like.

Example

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 DBU 13.74 g in 100 mL 1-pentanol , stirred at an internal temperature of 125°C for 24 hours. Thereafter, 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 a green powder. The obtained compound confirmed that it was the compound (a-1) represented by the objective following formula (a-1) from the following analysis result.

MS: (EI) m/z 2245M+)

-Elemental analysis value: actual 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 thus obtained compound exhibited a maximum absorption at 734.5 nm, and the gram extinction coefficient was 6.75×10 ⁴ mL/g·cm.

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

<Synthesis Example 2> Synthesis of phthalocyanine compound (a-2)

Instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1, 4,7-bis(4-methyl Except using 18.6 g of thoxybutyl)-1,3-diiminoisoindoline, it carried out similarly to the synthesis example 1, and obtained 14.5 g of green powders. The obtained compound confirmed that it was the compound (a-2) represented by the objective following formula (a-2) from the following analysis result.

MS: (EI) m/z 1267M+)

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

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

The toluene solution of the thus obtained compound exhibited a maximum absorption at 734.0 nm, and the gram extinction coefficient was 1.21×10 ⁵ mL/g·cm.

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

Instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1, 4,7-bis(4-( Except using 29.4 g of 3-methoxyphenoxy) butyl) -1,3-diiminoisoindoline, it carried out similarly to Synthesis Example 1, and obtained 5.9 g of green powder. The obtained compound confirmed that it was the compound (a-3) represented by the objective following formula (a-3) from the following analysis result.

·MS: (EI) m/z 2003M+)

-Elemental analysis value: actual 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 thus obtained compound exhibited a 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)

Instead of 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1, 4,7-bis(4-( Except using 28.0 g of 2-fluorophenoxy) butyl) -1, 3- diiminoisoindoline, it carried out similarly to Synthesis Example 1, and obtained 11.2 g of green powder. The obtained compound confirmed that it was the compound (a-4) represented by the objective following formula (a-4) from the following analysis result.

MS: (EI) m/z 1908M+)

- Elemental analysis value: actual 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 thus obtained compound exhibited a 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 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline in Synthesis Example 1, 4,7-bis(4-( 31.0 g of green powder was obtained in the same manner as in Synthesis Example 1 except that 38.8 g of (1,6-dimethoxynaphthalen-2-yl)oxy)butyl)-1,3-diiminoisoindoline was used. The obtained compound confirmed that it was the compound (a-5) represented by the objective following formula (a-5) from the following analysis result.

MS: (EI) m/z 　2645M+)

-Elemental analysis value: actual 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 thus obtained compound exhibited a 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 32.9 g of 4,7-bis(4-(2,6-dimethoxyphenoxy)butyl)-1,3-diiminoisoindoline 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-(2,6-dimethoxyphenoxy)butyl) Except using 16.5 g of -1,3-diiminoisoindoline, it carried out similarly to Synthesis Example 1, and obtained 28.1 g of green powder. It was confirmed by LC-MS that the obtained compound was the compound (a-6) represented by the objective following formula (a-6) by m/z agreement of each component.

The toluene solution of the thus obtained compound exhibited a maximum absorption at 735.5 nm, and the gram extinction coefficient was 6.30×10 ⁴ mL/g·cm.

In addition, all said phthalocyanine compounds (a-1) - (a-6) are phthalocyanine compounds represented by said Formula (1).

<Synthesis Example 7> Synthesis of phthalocyanine compound (a'-1)

According to the description of Example (65) of Japanese Patent Application Laid-Open No. Hei 02-138382, phthalocyanine (a'-1) (maximum absorption wavelength 725 nm) for a comparative example represented by the following formula was synthesized.

<Synthesis Example 8> Synthesis of phthalocyanine compound (a'-2)

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

<Synthesis Example 9> Synthesis of phthalocyanine compound (a'-3)

Using the method described in paragraphs [0020] to [0025] (Example 1) of Japanese Patent Application Laid-Open No. Hei 05-25177, other phthalocyanine compounds (a'-3) for dyes represented by the following formula (maximum absorption) wavelength 692 nm) was synthesized.

<Synthesis Example 10> Synthesis of cesium tungsten oxide powder

_{A cesium tungsten oxide (Cs 0.33} WO ₃ ) powder was synthesized using the method described in paragraph [0113] of Japanese Patent No. 4096205.

<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 methacrylate 20 parts by mass of acrylic acid was 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 prepared. After nitrogen purge in the reaction vessel, heating at 80° C. for 5 hours while stirring and nitrogen bubbling, a solution containing binder resin (b-1) (binder resin solution (B-1): 35 mass % solid content) got it About the obtained binder resin (b-1), a Showa Denko gel permeation chromatography (GPC) apparatus (GPC-104 type, column: 3 pieces of Showa Denko Corporation LF-604 and KF-602 were combined, and developed As a result of measuring the molecular weight in terms of polystyrene using 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 addition, in this synthesis example, it can be considered that the input ratio (mass ratio) of each monomer and content ratio (mass ratio) of the structural unit derived from each monomer in the obtained binder resin are substantially the same (the following synthesis). The same is true for Example 14).

<Synthesis Example 12> Synthesis of binder resin (b-2)

200 mass parts of propylene glycol monomethyl ether was put into the flask provided with the cooling tube and the stirrer, and the temperature was raised to 80 degreeC. 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 is added dropwise over 3 hours, and the temperature is maintained after dropping. and polymerized for 3 hours. Then, the temperature of the reaction solution was heated up to 100-120 degreeC, and reaction was performed for further 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. and reacted for 9 hours, which is represented by the following formula A solution (binder resin solution (B-2): solid content concentration of 40% by mass) containing binder resin (b-2) was obtained. As a result of measuring the molecular weight similarly to Synthesis Example 11 about the obtained binder resin, the weight average molecular weight (Mw) was 15100, the number average molecular weight (Mn) was 7000, and Mw/Mn was 2.16.

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

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

200 mass parts of propylene glycol monomethyl ether was put into the flask provided with the cooling tube and the stirrer, and the temperature was raised to 80 degreeC. At the same temperature, a mixed solution of 200 parts by mass of propylene glycol monomethyl ether, 67 parts by mass of methacrylic acid, 33 parts by mass of N-cyclohexylmaleimide and 5 parts by mass of 2,2'-azoisobutyronitrile was added in 3 hours. It was dripped over and superposed|polymerized for 3 hours by maintaining the temperature after dripping. Then, the temperature of the reaction solution was raised to 100-120 degreeC, and reaction was performed further 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, and the temperature is raised to 110° C. and reacted for 30 hours, resulting in the following formula The solution (binder resin solution (B-3): 40 mass % of solid content concentration) containing binder resin (b-3) was obtained. As a result of measuring the molecular weight similarly to Synthesis Example 11 about the obtained binder resin, the weight average molecular weight (Mw) was 17000, the number average molecular weight (Mn) was 7700, and Mw/Mn was 2.21.

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

<Synthesis Example 14> Synthesis of binder resin (b-4)

5 parts by mass of 2,2-azobisisobutyronitrile, 140 parts by mass of 3-methoxymethylpropionate, and 60 parts by mass of propylene glycol monomethyl ether were put into a flask provided with a cooling tube and a stirrer, and further methacrylic acid After putting 32 parts by mass of glycidyl, 40 parts by mass of 3-methacryloxypropyltriethoxysilane, 11 parts by mass of benzyl methacrylate, 3 parts by mass of n-butyl methacrylate and 14 parts by mass of methacrylic acid, nitrogen substitution , while stirring slowly, the temperature of the solution was raised to 80 °C. The solution containing binder resin (b-4) (the following binder resin solution (B-4) solid content concentration 35 mass %) was obtained by superposing|polymerizing at this temperature for 5 hours. About the obtained binder resin, when molecular weight was measured similarly to 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, 30 parts by mass of PME-200 (a polymer of methoxypolyethylene glycol monomethacrylate and a monomer represented by CH ₂ =C(CH ₃ )COO(C ₂ H ₄ O) _n -CH ₃ (n≒4)) in a batch The polymerization was carried out to obtain a reaction solution containing a random copolymer. Then, the reaction solution was quenched using methanol, and the obtained reaction solution was wash|cleaned with 7 mass % sodium hydrogencarbonate aqueous solution, then water. Then, the dispersing agent solution (D-2) containing a dispersing agent (d-2) was obtained with a yield of 80 mass % by performing solvent substitution to propylene glycol monomethyl ether acetate (PGMEA). As for the amine value of the obtained dispersing agent (d-2), 160 mgKOH/g, Mw was 9500, Mw/Mn was 1.21, and the solid content of the dispersing agent solution (D-2) was 39.6 mass %.

[Preparation Example 1] Preparation of dispersion (C-1)

25.00 parts by mass of the cesium tungsten oxide, 13.30 parts by mass of "BYK-LPN6919" (solid content concentration of 60 mass %, amine value of 120 mgKOH/g) manufactured by Big Chemis as a dispersant (d-1), and cyclopentanone as a solvent (dispersion medium) (CPN) 61.70 parts by mass was prepared. These were filled in a container together with 2000 mass parts of 0.1 mm diameter zirconia beads, and the dispersion liquid (C-1) whose average particle diameter (D50) is 19 nm was obtained by performing dispersion|distribution with a paint shaker. In addition, the average particle diameter was measured by the DLS method using the light scattering measuring apparatus ("ALV-5000" by German ALV company).

[Preparation Example 2] Preparation of dispersion (C-2)

The dispersion liquid (C-2) whose average particle diameter is 19 nm was obtained like Preparation Example 1 except having changed 20.20 mass parts of dispersing agent solutions (D-2), and having changed the solvent into CPN 54.80 mass parts.

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

5.00 parts by mass of the phthalocyanine compound (a-1) and 95.00 parts by mass of CPN as a solvent were measured and taken in a container, and mixed with a stirrer. The dye solution (A-1) was obtained by pressure-filtering the obtained solution under constant pressure conditions of 0.05 Mpa using a 0.2-micrometer-made polytetrafluoroethylene (PTFE) filter. In addition, each dye solution described in Table 1 was carried out in the same manner as above except that phthalocyanine compounds (a-2) to (a-6), (a-8) and (a-9) were used as the phthalocyanine compound, respectively. (A-2) to (A-6), (A-8) and (A-9) were obtained.

About the dye solution (A-7), it carried out similarly, and prepared it except having used CPN 94.30 mass parts as 4.50 mass parts of phthalocyanine compound (a-1), 1.20 mass parts of phthalocyanine compound (a'-3), and a solvent.

[Example 1]

20.00 parts by mass of the dispersion (C-1), 23.15 parts by mass of the dye solution (A-1), 21.01 parts by mass of the binder resin solution (B-1), "KAYARAD DPHA" (dipentaeryth) by Nippon Kayaku as a polymerizable compound Mixture of ritol 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, Neos' FTX-218D as a surfactant "(Fluorine-based surfactant) 0.05 parts by mass, Showa Denko's "Carenz MT PE1" (polyfunctional thiol) 0.31 parts by mass as a reaction modifier, BASF's "Irganox1010" (phenolic antioxidant) 0.10 parts by mass as an antioxidant And 25.71 mass parts of cyclopentanone (CNP) as a solvent were measured and taken in a container, and it mixed with a stirrer. The composition of Example 1 was obtained by pressure-filtering about 100 mL of this mixture under constant pressure conditions of 0.05 Mpa using a 0.5-micrometer PTFE filter.

[Examples 2 to 13, Comparative Examples 1 to 3]

The types and blending amounts (parts by mass) of the dispersion, the dye solution and the binder resin solution, and the blending amounts (parts by mass) of the polymerizable compound, polymerization initiator, surfactant, reaction modifier, antioxidant and solvent are as shown in Table 1. Except that, it carried out similarly to Example 1, and obtained each composition of Examples 2-13 and Comparative Examples 1-3. In addition, in Table 1, the kind of [A] phthalocyanine compound, [B] binder resin, [C] infrared shielding agent, [D] dispersing agent, and other pigment|dye in each obtained composition, and content in solid content are also shown. "CsWO" in Table 1 represents the cesium tungsten oxide (Cs _0.33 WO ₃ ) obtained in Synthesis Example 10.

[evaluation]

The following evaluation was performed using each obtained composition. An evaluation result is shown in Table 1.

Each composition was apply|coated by spin coating so that it might become a predetermined|prescribed film thickness on a glass substrate. Then, the coating film was heated at 100 degreeC for 120 second, and exposure was performed so that it might become 500 mJ/cm<2> with an i-line stepper. Then, by heating at 220 degreeC for 300 second, the infrared shielding film of 2.0-4.0 micrometers in average film thickness was produced on the glass substrate. Each average film thickness is shown in Table 1. In addition, the film thickness was measured with the stylus-type step meter ("Alpha Step IQ" by Yamato Chemical Co., Ltd.). Next, the transmittance|permeability in each wavelength region of the infrared ray shielding film produced on the said glass substrate was measured in contrast with a glass substrate using the spectrophotometer ("V-7300" by Nippon Bunko Corporation). From the obtained spectrum, evaluation was performed by the following evaluation criteria.

(Visible light transmittance)

The average transmittance of 430-580 nm was calculated. When the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film decreases. In addition, the following references|standards evaluated the said average transmittance|permeability.

A: 80% or more

B: 70% or more and less than 80%

C: less than 70%

(Visible transmission window range)

The transmittance|permeability in the range of 430-580 nm calculated|required the range used as 70% or more continuously. When the range used as 70% or more continuously is 175 nm or more and it uses as an infrared-shielding film, since it has high sensitivity, it is estimated that practicability is high. In addition, about the said visible transmission window range, the following reference|standard evaluated.

A: 200 nm or more

B: 175 nm or more and less than 200 nm

C: less than 175 nm

(infrared shielding range)

The transmittance|permeability in the range of 700-800 nm calculated|required the range used as 20 % or less continuously. When the range used as 20% or less continuously is 20 nm or more, when it uses as an infrared-shielding film, since it has a high noise shielding function, it is estimated that practicability is high. In addition, the following references|standards evaluated the said infrared-shielding range.

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 at which the transmittance becomes 80% or more is (X), and the shortest wavelength at which the transmittance becomes 20% or less is (Y), and the average Off-Slope (Z) is calculated in this way. When the average Off-Slope is 0.45 or more, when it is used as an infrared shielding film, it becomes possible to improve the color reproducibility and noise shielding function of the image obtained, and it is estimated that the practicality is high. In addition, the following reference|standard evaluated the said average Off-Slope.

(Z)=60/((Y)-(X))

AA: 0.60 or higher

A: More than 0.50 and less than 0.60

B: 0.45 or more and less than 0.50

C: less than 0.45

(Heat resistance)

The infrared shielding film produced on the glass substrate was heated at 260° C. for 300 seconds using a hot plate, and the transmittance in each wavelength region before and after heating was measured with a spectrophotometer (“V-7300” manufactured by Nippon Bunko Corporation). was used and measured in comparison with a glass substrate. At this time, the absorbance at the wavelength where the transmittance is the lowest in the range of 700-800 nm of the prepared infrared shielding film (A1), the absorbance after heating at 260°C at the same wavelength (A2), the absorbance retention rate = 100x As (A1)/(A2), the following reference|standard evaluated the heat resistance of 260 degreeC. When the retention ratio is 30% or more, when it is used as an infrared shielding film, it becomes possible to maintain high heat resistance by using together with a protective film etc., and it is estimated that practicability is high. In addition, the following references|standards evaluated the said retention rate.

AA: 90% or more

A: 60% or more and less than 90%

B: 30% or more and less than 60%

C: less than 30%

(fault suppression)

Each composition was apply|coated by the spin coating method on a silicon substrate, this coating film was hardened, and the cured film with a film thickness of about 1 micrometer was formed. The defect density (Defect density) of the cured film was measured using the defect / foreign material inspection apparatus ("KLA 2351" by KLA-Tencor). It can be judged that defect suppression property is high, so that the value of this defect density is small. In addition, a defect refers to the detection point used as 1 micrometer or more in size. Based on the said defect density, the following references|standards evaluated defect suppression.

A: 10/cm2 or less

B: More than 10/cm2 and less than 50/cm2

C: more than 50/cm2

(PCD stability)

Each composition was applied on a silicon substrate by spin coating, and a coating film having a film thickness of about 1 µm was formed in a state in which the coating film was not cured. The defect density (Defect density) of the coating film was measured using the defect / foreign material inspection apparatus ("KLA 2351" by KLA-Tencor). Subsequently, the defect density of the coating film is measured at regular time intervals, the time when the number of defects increases by 20% or more from the initial value is measured, and the stability after application after the coating film is evaluated (PCD: Post Coating Delay) stability did. As for PCD stability, it is estimated that practicality is high, so that a value is large.

A: More than 24 hours

B: More than 12 hours and less than 24 hours

C: less than 12 hours

As shown in Table 1, any of Examples 1 to 13 showed good evaluation of visible light transmittance, visible light transmission window range, infrared shielding range, average off-slope, heat resistance, defect suppression property, and PCD stability. Moreover, among Examples using the phthalocyanine compound represented by the said Formula (1), Examples 1, 3-6 using the phthalocyanine compound (a-1, a-3-a-6) in which R has a substituent are R It turns out that it has high heat resistance compared with Example 2 using the phthalocyanine compound (a-2) which does not have this substituent. In addition, it can be seen that among the above Examples in which R is a phthalocyanine compound having a substituent, the visible light transmittance is also good in Examples 1, 3 and 4.

(Industrial Applicability)

The composition for optical sensors of this invention can be used suitably as a formation material of optical filters of optical sensors, such as a solid-state image sensor.

Claims (9)

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

(in formula (1), a plurality of R is each independently a substituent or unsubstituted alkyl group, or a substituent or unsubstituted aryl group; a plurality of Xs are each independently a hydrogen atom, a halogen atom or an alkyl group; a 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; A plurality of n is each independently an integer of 3 to 6) According to claim 1,
The plurality of R is each independently an alkyl group having a substituent or an aryl group having a substituent, the composition for an optical sensor. 3. The method of claim 1 or 2,
The composition for an optical sensor wherein the binder resin has an oxiranyl group, an oxetanyl group, a (meth)acryloyl group, an alkoxysilyl group, or a combination thereof. 4. The method according to any one of claims 1 to 3,
The composition for optical sensors in which the said binder resin has a ring structure in a main chain. The phthalocyanine compound represented by following formula (2)
A composition for an optical sensor containing a.

(in formula (2), a plurality of R's are each independently an alkyl group having a substituent or an aryl group having a substituent; a plurality of X's are each independently a hydrogen atom, a halogen atom or an alkyl group; may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded; M is two hydrogen atoms, a divalent metal atom, or a derivative of a trivalent or tetravalent metal atom; Independently, it is an integer from 3 to 6) 6. The method according to any one of claims 1 to 5,
The composition for optical sensors, wherein the substituents of the alkyl group and the aryl group each represented by the plurality of R are groups having a hetero atom. 7. The method of claim 6,
The composition for an optical sensor wherein the substituent is a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, or a combination thereof. 8. The method according to any one of claims 1 to 7,
An infrared shielding agent that is a metal oxide, a copper compound (excluding the above phthalocyanine compound), or a combination thereof
A composition for an optical sensor further comprising a. 9. The method of claim 8,
The composition for optical sensors in which the said metal oxide is cesium tungsten oxide.