KR20150143640A - Near-infrared-absorbing composition, near-infrared cut-off filter and production method using same, and camera module and method for producing same - Google Patents

Abstract

A near infrared ray absorbing composition capable of forming a cured film having excellent heat resistance while maintaining a high near infrared ray shielding property, a near infrared ray shielding filter using the same, a camera module, and a manufacturing method thereof. A compound obtained by a reaction of a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and an acid group or a salt thereof with a copper component.

Description

TECHNICAL FIELD [0001] The present invention relates to a near infrared ray absorbent composition, a near infrared ray absorbing composition using the same, a manufacturing method thereof, and a camera module and a manufacturing method thereof. }

The present invention relates to a near-infrared light absorbing composition, a near-infrared ray blocking filter using the same, a method of manufacturing the same, a camera module, and a manufacturing method thereof.

2. Description of the Related Art A CCD or CMOS image sensor, which is a solid-state image pickup device for a color image, is used for a video camera, a digital still camera, or a mobile phone having a camera function. Since the solid-state image pickup device uses a silicon photodiode having sensitivity to near-infrared rays in the light-receiving portion, it is necessary to perform visibility correction, and a near-infrared cutoff filter (hereinafter also referred to as an IR cutoff filter) is often used.

As a material of the near-infrared ray cut filter, Patent Document 1 discloses a material for infrared blocking property which is obtained by adding a metal compound to a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenic unsaturated bond Discloses an infrared shielding film comprising a resin.

Patent Document 1: JP-A-2010-134457

Here, when examining the infrared blocking resin disclosed in Patent Document 1, it was found that the heat resistance is insufficient.

An object of the present invention is to provide a near infrared absorbing composition capable of forming a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property.

As a result of intensive studies conducted by the present inventors, it has been found that by employing a compound obtained by reacting a polymer (A1) having at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in its main chain with an acid group or a salt thereof and a copper component, I found that I could solve the problem. Concretely, the above problem is solved by the following means <1>, preferably by <2> to <17>.

<1> A near infrared ray absorbing composition comprising a compound obtained by reacting a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and an acid group or a salt thereof with a copper component.

<2> The near infrared absorbing composition according to <1>, wherein the polymer (A1) comprises a constitutional unit represented by the following formula (A1-1);

[Chemical Formula 1]

In the formula (A1-1), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y ¹ represents a single bond or a divalent linking group, and X ¹ represents an acid group or a salt thereof.

<3> The near infrared absorbing composition according to <1> or <2>, wherein the polymer (A1) comprises a constitutional unit represented by the following formula (A1-2)

(2)

Formula (A1-2) of, Ar ² represents an aromatic hydrocarbon group and / or aromatic heterocyclic group, Y ² denotes a single bond or a divalent connecting group, X ² represents an acid group or a salt thereof, Y ³ represents a single _{bond, -O-, -S-, -SO 2 -} , -CO-, -C (= O) O-, -OC (= O) O-, -P (= O) R 0 -, -CR 1 R ² - or -C (= O) NR ³ -; R ⁰ represents a hydrogen atom, a hydrocarbon group, or a hydroxyl group; R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group; R ³ represents a hydrogen atom or a hydrocarbon group.

The divalent linking group may be a linear, branched or cyclic alkylene group, an arylene group, -O-, -S-, -C (= O) -, -C (= O) O-, The near infrared absorbing composition according to < 2 > or < 3 >

<5> The method according to any one of <1> to <4>, wherein the acid group or its salt is selected from at least one member selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, a phosphonic acid and a salt thereof, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

<6> The near infrared ray absorbing composition according to any one of <1> to <5>, wherein the acid group or a salt thereof is selected from at least one selected from a carboxylic acid group and a salt thereof, and a sulfonic acid group and a salt thereof.

<7> The near infrared absorbing composition according to any one of <1> to <6>, wherein the polymer (A1) has a weight average molecular weight of 1,000 to 10,000.

<8> The near infrared absorbing composition according to any one of <1> to <7>, further containing water.

<9> A near-infrared absorbing composition comprising a copper complex having an acid group ion site of a polymer (A2) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and containing an acid group ion as a ligand.

&Lt; 10 > A polymer obtained by reacting a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain with an acid group or a salt thereof and a copper component,

A low molecular weight compound containing an acid group or a salt thereof and a copper complex obtained by a reaction of a copper component

Absorbent composition.

<11> The near infrared absorbing composition according to <10>, wherein the molecular weight of the low molecular weight compound is 1000 or less.

<12> The near infrared absorbing composition according to <10> or <11>, wherein the low molecular compound comprises at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom.

<13> A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of <1> to <12>.

<14> The near infrared ray blocking filter according to <13>, wherein a rate of change in absorbance ratio obtained by the following equation before and after heating at 200 ° C for 5 minutes is 5% or less.

[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]

Here, the term "absorbance ratio" refers to a value obtained by dividing the maximum absorbance at a wavelength of 700 to 1400 nm by the minimum absorbance at a wavelength of 400 to 700 nm.

<15> A method for manufacturing a near-infrared light blocking filter, comprising the step of forming a film on the light receiving side of a solid-state imaging element substrate by applying the near infrared absorbing composition according to any one of <1> to <12>.

<16> A camera module having a solid-state imaging element substrate and a near-infrared ray blocking filter disposed on a light receiving side of the solid-state imaging element substrate, wherein the near-infrared ray blocking filter is a near-infrared ray blocking filter described in <13> or <14>.

A manufacturing method of a camera module having a solid-state imaging element substrate and a near-infrared cut-off filter disposed on a light-receiving side of the solid-state imaging element substrate is characterized in that, on the light-receiving side of the solid-state imaging element substrate, And a step of forming a film by applying the near infrared absorbing composition described in the first aspect of the present invention.

According to the present invention, it becomes possible to provide a cured film excellent in heat resistance while maintaining a high near infrared ray shielding property.

1 is an image diagram showing an example of a compound containing a polymer (A2) and a copper ion in the present invention.
2 is a schematic sectional view showing a configuration of a camera module including a solid-state image pickup device according to an embodiment of the present invention.
3 is a schematic cross-sectional view of a solid-state imaging element substrate according to an embodiment of the present invention.

Hereinafter, the contents of the present invention will be described in detail.

In the present specification, "~" is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacryl, "(meth) acryloyl" Represents &lt; / RTI &gt;

As used herein, "monomer" and "monomer" are synonyms, and "polymer" and "polymer" are synonyms.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent.

The near infrared ray in the present invention means the maximum absorption wavelength region of 700 to 2500 nm, particularly 700 to 1000 nm.

The near infrared ray absorbency in the present invention means that the near infrared ray region has the maximum absorption wavelength.

The main chain of the polymer in the present invention refers to an atom or an atomic group necessary for forming a skeleton (long chain) of a polymer. When a part or the whole of the skeleton is a cyclic group (for example, an aryl group) As part of the prayer chain. The atom directly bonded to the main chain is also part of the main chain. The side chain of the polymer in the present invention refers to a portion other than the main chain. However, the side chain is also a functional group directly bonded to the main chain (for example, an acid group or salt thereof described later).

<Near infrared absorptive composition of the present invention>

The first near infrared absorbing composition of the present invention is characterized by comprising a compound obtained by reacting a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and an acid group or a salt thereof with a copper component do.

The second near IR absorptive composition of the present invention is a composition comprising a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and having an acid group or a salt thereof and a compound obtained by the reaction of a copper component, A low molecular weight compound containing a salt and a copper complex obtained by a reaction of a copper component.

Since the near infrared absorbing composition of the present invention contains a compound obtained by the reaction of the polymer (A1) with a copper component, a cured film having excellent heat resistance can be formed while maintaining a high near infrared ray shielding property as a cured film. This reason is presumed, but is considered as follows.

The compound obtained by the reaction of the polymer (A1) with the copper component is, for example, a polymer (A2) containing an acid group ion and a compound containing a copper ion. In a preferred embodiment, . &Lt; / RTI &gt; 1 is an image showing an example of a polymer (A2) containing an acid group ion and a compound containing a copper ion, wherein 1 denotes a polymer (A2) containing an acid group ion and a compound containing a copper ion, 2 3 represents a main chain of the polymer (A2), 4 represents a side chain of the polymer (A2), and 5 represents an acid ion site derived from an acid group or a salt thereof. In the present invention, the acid ion site 5 bonds to the copper ion 2 (for example, coordinate bond) to form a crosslinked structure between the side chains 4 of the polymer A2 starting from copper . With such a constitution, even when heated, it is presumed that the structure of the compound (1) is hardly collapsed and, as a result, a cured film excellent in heat resistance is obtained. Since the polymer (A2) has at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in its main chain (3), a cured film excellent in heat resistance can be obtained.

Further, in the present invention, by using the compound obtained by the reaction of the polymer (A1) and the copper component, the content of copper in the composition can be increased, and copper is not easily removed even when heated.

The content of copper in the near infrared absorbing composition containing the compound obtained by reacting the polymer (A1) with the copper component is preferably 5 to 25% by mass, more preferably 7 to 20% by mass, and more preferably 8 to 15% Is more preferable.

The content of the compound obtained by the reaction of the polymer (A1) with the copper component is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total solid content in the composition of the present invention.

The content of the compound obtained by the reaction of the polymer (A1) and the copper component in the second near infrared absorbing composition of the present invention is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, relative to the total solid content in the composition , More preferably from 15 to 70 mass%, and even more preferably from 20 to 70 mass%.

The reaction conditions of the compound obtained by the reaction of the polymer (A1) with the copper component are not particularly limited, but for example, the reaction conditions are 0 to 140 ° C for 10 minutes or more.

<< Copper Ingredients >>

As the copper component, a compound containing divalent copper is more preferable. The copper content in the copper component used in the present invention is preferably 2 to 90 mass%, and more preferably 10 to 70 mass%. The copper component may be used alone, or two or more copper components may be used.

As the copper component used in the present invention, for example, a compound containing copper or copper can be used. As the compound containing copper, for example, copper oxide or copper salt can be used. The copper salt is preferably a monovalent or divalent copper, and more preferably a divalent copper. Examples of the copper salts include copper salts such as copper hydroxide, copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, (Meth) acrylate and copper perchlorate are exemplified, and copper hydroxide, copper acetate, copper chloride, copper sulfate, copper benzoate and copper (meth) acrylate are more preferable, and copper hydroxide, copper acetate and copper sulfate Is particularly preferable.

The amount of the copper component to be reacted with the polymer (A1) is preferably 0.01 to 1 equivalent, more preferably 0.1 to 0.6 equivalent, and more preferably 0.4 to 0.5 equivalent per 1 equivalent of the acid group or the salt thereof of the polymer (A1) Do. When the amount of copper in the copper component is within this range, a cured film having higher near infrared ray shielding property tends to be obtained.

<< Polymer (A1) having an aromatic hydrocarbon group and / or aromatic heterocyclic group in its main chain and having an acid group or a salt thereof >>

The polymer (A1) has an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain. The polymer (A1) may contain at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain, or may have two or more kinds thereof. As the polymer (A1), only one type may be used, but two or more types may be used.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, particularly preferably a phenyl group, a naphthyl group or a biphenyl group desirable. The aromatic hydrocarbon group may be monocyclic or polycyclic, but monocyclic is preferred.

As the aromatic heterocyclic group, for example, an aromatic heterocyclic group having 2 to 30 carbon atoms can be used. The aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The aromatic heterocyclic group is a monocyclic or condensed ring, and examples thereof include monocyclic or condensed rings having 2 to 8 condensed rings. Examples of the hetero atom contained in the heterocycle include nitrogen, oxygen and sulfur atoms, and nitrogen or oxygen is preferable.

When the aromatic hydrocarbon group and / or the aromatic heterocyclic group has the substituent T, examples of the substituent T include an alkyl group, a polymerizable group (preferably a polymerizable group having a carbon-carbon double bond), a halogen atom ( A fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a carboxylic acid ester group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloyloxy group, an ether group, a sulfonyl group, An acyl group, a hydroxyl group, a carboxyl group, an aralkyl group and the like are exemplified, and an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms) is preferable.

Particularly, the polymer (A1) is preferably at least one selected from the group consisting of a polyether sulfone polymer, polysulfone polymer, polyether ketone polymer, polyphenylene ether polymer, polyimide polymer, polybenzimidazole polymer, At least one polymer selected from a phenol resin-based polymer, a polycarbonate-based polymer, a polyamide-based polymer, and a polyester-based polymer. Examples of the respective polymers are shown below.

A polymer having a main chain structure represented by (-O-Ph-SO ₂ -Ph-) (Ph represents a phenylene group, the same applies hereinafter)

Poly sulfone-based polymer: a polymer having a (-O-Ph-Ph-O -Ph-SO 2 -Ph-) a main chain structure represented by

A polymer having a main chain structure represented by a polyether ketone polymer: (-O-Ph-O-Ph-C (= O) -Ph-)

A polymer having a main chain structure represented by a polyphenylene ether polymer: (-Ph-O-, -Ph-S-)

Polyphenylene polymer: A polymer having a backbone structure represented by (-Ph-)

Phenol resin-based polymer: a polymer having a backbone structure represented by (-Ph (OH) -CH ₂ -)

Polymer having a main chain structure represented by a polycarbonate-based polymer: (-Ph-O-C (= O) -O-)

Examples of the polyamide-based polymer include polymers having a backbone structure represented by (-Ph-C (= O) -NH-)

As the polyester polymer, for example, a polymer having a backbone structure represented by (-Ph-C (= O) O-)

Examples of the polyether sulfone type polymer, polysulfone type polymer and polyether ketone type polymer include polymers having a backbone structure described in Japanese Patent Application Laid-Open No. 2006-310068, paragraph 0022, and Japanese Patent Application Laid-Open No. 2008-27890, paragraph 0028 , The contents of which are incorporated herein by reference.

As the polyimide-based polymer, the main chain structure described in paragraphs 0047 to 0058 of Japanese Patent Application Laid-Open No. 2002-367627 and 1988 to 0019 of Japanese Patent Application Laid-Open No. 2004-35891 may be taken into consideration and these contents are incorporated herein by reference .

The polymer (A1) contains an acid group or a salt thereof, but the acid group or a salt thereof may be one kind or two or more kinds.

The acid group of the polymer (A1) is not particularly limited as long as it is capable of reacting with the above-mentioned copper component, but it is preferable to coordinate bond with the copper component. For example, an acid group having an acid dissociation constant (pKa) of 5 or less can be enumerated, and a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and an imidic acid group are preferable.

Examples of the atoms or atomic groups constituting the acid group salt used in the present invention include atomic groups such as metal atoms (particularly alkali metal atoms) such as sodium, tetrabutylammonium and the like, preferably metal atoms and more preferably alkali metal atoms .

In the polymer (A1), the acid group or a salt thereof may be included in at least one of the main chain and the side chain thereof, and is preferably contained at least in the side chain. Particularly, in the polymer (A1), it is preferable that the acid group or its salt is bonded to the aromatic hydrocarbon group and / or the aromatic heterocyclic group directly or via a linking group.

Among the acid groups or salts thereof, those containing at least one member selected from, for example, carboxylic acid groups and salts thereof, phosphoric acid groups and salts thereof, phosphonic acids and salts thereof, and sulfonic acid groups and salts thereof are preferable.

The acid value of the polymer (A1) is preferably 1.5 meq / g or more, more preferably 2.0 to 7.0 meq / g.

It is preferable that 99 mol% or more of the total acid groups in the polymer (A1) is at least one selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, a phosphonic acid and a salt thereof, and a sulfonic acid group and a salt thereof. In particular, 99 mol% or more of the total acid groups in the polymer (A1) are preferably at least one selected from a carboxylic acid group and a salt thereof, and a sulfonic acid group and a salt thereof.

The polymer (A1) preferably contains a structural unit represented by the following formula (A1-1), more preferably a structural unit represented by the following formula (A1-2).

(3)

(Formula (A1-1) and formula (A1-2) of, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y ¹ and Y ² are each independently a single bond or indicates a divalent linking group, X ¹ and X ² represents an acid group or a salt thereof are each independently formula (A1-2) of the, Y ³ represents a single _{bond, -O-, -S-, -SO 2 -} , - -CO (= O) O-, -OC (= O) O-, -P (= O) R ⁰ - (R ⁰ represents a hydrogen atom, a hydrocarbon group or a hydroxyl group) CR ¹ R ² - (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group) or -C (= O) NR ³ - (R ³ represents a hydrogen atom or a hydrocarbon group).

In the formula (A1-1) and the formula (A1-2), when Ar ¹ represents an aromatic hydrocarbon group, it is the same as the above-mentioned aromatic hydrocarbon group and the preferable range is also the same. When Ar ¹ represents an aromatic heterocyclic group, it is in agreement with the above-described aromatic heterocyclic group, and the preferable range thereof is also the same.

Ar ¹ may have a substituent other than -Y ¹ -X ¹ in formula (A1-1) and Ar ² in addition to -Y ² -X ² in formula (A1-2). When Ar ¹ and Ar ² have a substituent, the substituent is the same as the above-mentioned substituent T, and the preferable range is also the same.

In the formula (A1-1), Y ¹ and Y ² are preferably a single bond. When Y ¹ and Y ² represent a divalent linking group, examples of the divalent linking group include a hydrocarbon group, an aromatic heterocyclic group, -O-, -S-, -SO ₂ -, -CO-, -C (= O-, -OC (= O) -, -SO ₂ -, -NX- (wherein X represents a hydrogen atom or an alkyl group and preferably a hydrogen atom), -C (R ^Y1 ) (R ^Y2 ) And a group formed by a combination of these. Here, R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

Examples of the hydrocarbon group include linear, branched or cyclic alkylene groups and arylene groups. The straight chain alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. The branched alkylene group is preferably an alkylene group having 3 to 20 carbon atoms, more preferably an alkylene group having 3 to 10 carbon atoms, and still more preferably an alkylene group having 3 to 6 carbon atoms. The cyclic alkylene group may be either monocyclic or polycyclic. The cyclic alkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 10 carbon atoms, and still more preferably a cycloalkylene group having 6 to 10 carbon atoms. These straight-chain, branched or cyclic alkylene groups may have hydrogen atoms in the alkylene group substituted by fluorine atoms.

The arylene group is preferably an arylene group having 6 to 18 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group.

The aromatic heterocyclic group is not particularly limited, but a 5-membered ring or a 6-membered ring is preferable. The aromatic heterocyclic group may be a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and more preferably a condensed ring having 2 to 4 monocyclic or condensed rings.

Particularly, when Y ¹ and Y ² in the formulas (A1-1) and (A1-2) represent a divalent connecting group, a linear, branched or cyclic alkylene group, an arylene group, -O-, -S- , -CO-, -C (= O) O-, or a combination thereof. Particularly, -S-, -C (R ^X1 ) (R ^X2 ) - (wherein R ^X1 and R ^X2 each independently represents an alkyl group having 1 to 3 carbon atoms or a fluorine atom), alkyl having 1 to 3 carbon atoms Or a combination thereof.

Among the formulas (A1-1) and (A1-2), the acid groups or salts thereof represented by X ¹ and X ² are synonymous with the above-mentioned acid groups or salts thereof, and preferable ranges are also the same.

In the formula (A1-2), when Y ³ is represented by -P (= O) R ⁰ -, the hydrocarbon group as R ⁰ is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

When Y ³ is represented by -CR ¹ R ² -, the hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms. R ¹ and R ² may be connected to form a ring.

When Y ³ is represented by -C (═O) NR ³ -, the hydrocarbon group as R ³ is preferably any group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

The weight average molecular weight of the polymer (A1) is preferably 1,000 or more, more preferably 1,000 to 1,000,000, still more preferably 3,000 to 1,000,000, and particularly preferably 4,000 to 400,000. By setting the weight average molecular weight of the polymer (A1) within such a range, the moisture resistance of the resulting cured film tends to be further improved.

Specific examples of the polymer (A1) used in the present invention include, but are not limited to, the following compounds and salts of the following acid groups (for example, the above metal salts).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

The near infrared absorbing composition of the present invention may contain a compound obtained by reacting the polymer (A1) with a copper component, but may contain other near infrared absorbing compound, solvent, curing compound, binder polymer, surfactant, Component may be blended.

The near infrared absorbing composition of the present invention may contain a compound containing an acid group or its salt used for obtaining another near infrared absorbing compound described later.

<< Other Near Infrared Absorbing Compound >>

To the composition of the present invention, a near infrared absorbing compound other than the compound obtained by the reaction of the above-mentioned polymer (A1) with the copper component may be added for the purpose of further improving the near infrared absorbing ability. The other near infrared absorbing compound used in the present invention is not particularly limited as long as it has a maximum absorption wavelength in a range of 700 to 2500 nm, preferably 700 to 1000 nm (near infrared region), in the maximum absorption wavelength region.

As the other near infrared absorbing compound, a copper compound is preferable, and a copper complex is more preferable. When other near infrared absorbing compounds are blended, the ratio (mass ratio) of the compound obtained by the reaction between the polymer (A1) and the copper component to the other near infrared absorbing compound is preferably from 10:90 to 95: 5, more preferably from 20:80 To 90:10, and more preferably from 20:80 to 80:20.

The molecular weight of the other near infrared absorptive compound is not particularly limited, but is preferably 70 to 1000, more preferably 130 to 500.

When the other near infrared absorptive compound is a copper complex, the ligand L to be coordinated to copper is not particularly limited as long as it is capable of coordinating with copper ion, and examples thereof include sulfonic acid, carboxylic acid, phosphoric acid, phosphoric acid ester, phosphonic acid, Compounds having phosphonic acid, substituted phosphinic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, urethane, urea, alcohol, thiol and the like. Of these, carboxylic acid and sulfonic acid are preferable, and sulfonic acid is more preferable.

Specific examples of the copper complexes include a phosphorus-containing copper compound, a copper sulfonate compound, or a copper compound represented by the following formula (A). Specific examples of the phosphorus-containing copper compound include compounds described in WO2005 / 030898, page 5, line 27 to page 7, line 20, the contents of which are incorporated herein by reference.

Examples of the copper complexes include copper complexes represented by the following formula (A).

Cu (L) _n1 (X) _n2 ????? (A)

In the formula (A), L represents a ligand to be coordinated to copper, X is absent, or a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ , BPh ₄ (Ph represents a phenyl group), or an alcohol. n1 and n2 each independently represent an integer of 1 to 4;

The ligand L has a substituent containing C, N, O, S as an atom capable of coordinating to copper, more preferably a group having a lone pair of electrons such as N, O, S or the like. The group capable of coordination is not limited to one species within the molecule, and may include two or more species, may be dissociated, or may be resent. In contrast, X does not exist.

The copper complex is a copper compound for ligating the ligand to the copper of the central metal, and the copper is usually bivalent copper. For example, by mixing and reacting a compound or salt thereof as a ligand with respect to a copper component.

The compound or salt thereof to be a ligand is not particularly limited, and examples thereof include an organic acid compound (for example, a sulfonic acid compound, a carboxylic acid compound, a phosphate compound) or a salt thereof.

The compound or its salt as the ligand is preferably a compound containing an acid group or a salt thereof, and is preferably represented by the following general formula (i).

In general formula (i)

(11)

(In the general formula (i), R ¹ represents an organic group of n, X ¹ represents an acid group, and n represents an integer of 1 to 6.)

In the general formula (i), the n-valent organic group is preferably a hydrocarbon group or an oxyalkylene group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include a group having a halogen atom (preferably a fluorine atom), a (meth) acryloyl group or an unsaturated double bond.

When the hydrocarbon group is monovalent, an alkyl group or an aryl group is preferable, and an aryl group is more preferable. When divalent, an alkylene group, an arylene group and an oxyalkylene group are preferable, and an arylene group is more preferable. When the trivalent or more is present, it is preferable that the hydrocarbon groups correspond to the hydrocarbon groups.

The alkyl group and the alkylene group preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The number of carbon atoms of the aryl group and the arylene group is preferably 6 to 18, more preferably 6 to 12.

In the general formula (i), X ¹ is preferably at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom. X ¹ may be a single species or two or more species, but preferably two or more species.

In the general formula (i), n is preferably 1 to 3, more preferably 2 or 3, and more preferably 3.

The molecular weight of the compound or the salt thereof (acid group or a salt thereof) as the ligand is preferably 1,000 or less, more preferably 70 to 1,000, and still more preferably 70 to 500.

Preferred examples of the compound containing an acid group or a salt thereof include (1) a compound having at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom, more preferably (2) (3) an embodiment having a sulfonic acid group and a carboxylic acid group. In these embodiments, the infrared absorbing ability is more effectively exerted. Further, by using a compound having a sulfonic acid group and a carboxylic acid group, the color value can be further improved.

(1) Specific examples of the compound having at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom include the following. Specific examples of the sulfonic acid compound having a sulfonic acid group include specific examples of the sulfonic acid compound represented by the formula (I) described later. Among the compounds described in the following embodiments (2) and (3), the compounds corresponding to this embodiment are also preferable.

[Chemical Formula 12]

(2) Specific examples of the compound having at least two acid groups include the following. Among the compounds described in the later-described embodiment (3), preferred examples include compounds corresponding to this embodiment.

[Chemical Formula 13]

(3) Specific examples of the compound having a sulfonic acid group and a carboxylic acid group include the following. Specific examples of the compound having a sulfonic acid group and a carboxylic acid group represented by the formula (I) described later are also exemplified.

[Chemical Formula 14]

As another copper complex which can be used in the present invention, a copper complex obtained by reacting a sulfonic acid compound represented by the following formula (I) or a salt thereof with a copper component is also preferable.

In formula (I)

[Chemical Formula 15]

(In the formula (I), R ⁷ represents a monovalent organic group.)

Specific examples of monovalent organic groups include, but are not limited to, linear, branched or cyclic alkyl groups, alkenyl groups and aryl groups. Here, these groups may be substituted with a divalent linking group (e.g., an alkylene group, a cycloalkylene group, an arylene group, -O-, -S-, -CO-, -C (= O) O-, -OCO-, SO ₂ -, -NR- (R is a hydrogen atom or an alkyl group), etc.). The monovalent organic group may have a substituent.

As the straight-chain or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

The cyclic alkyl group may be monocyclic or polycyclic. The cyclic alkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms, and still more preferably a cycloalkyl group having 6 to 10 carbon atoms. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 8 carbon atoms is more preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.

The aryl group is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

Examples of the divalent linking group alkylene group, cycloalkylene group and arylene group include divalent linking groups derived by removing one hydrogen atom from the above-mentioned alkyl group, cycloalkyl group and aryl group.

Examples of the substituent which the monovalent organic group may have include an alkyl group and a polymerizable group such as a vinyl group, a (meth) acryloyl group, an epoxy group, an oxetane group and the like), a halogen atom, a carboxyl group, (For example, -CO ₂ CH ₃ ), a hydroxyl group, an amide group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group) and the like.

The molecular weight of the sulfonic acid compound represented by the following formula (I) or its salt is preferably 80 to 750, more preferably 80 to 600, and even more preferably 80 to 450.

Specific examples of the sulfonic acid compound represented by the formula (I) are shown below, but the present invention is not limited thereto.

[Chemical Formula 16]

[Chemical Formula 17]

The sulfonic acid compound that can be used in the present invention may be a commercially available sulfonic acid or may be synthesized by referring to a known method. Examples of the salt of the sulfonic acid compound that can be used in the present invention include a metal salt, and specific examples thereof include a sodium salt and a potassium salt.

Other copper complexes that can be used in the present invention include, in addition to those described above, copper complexes having a carboxylic acid as a ligand. As the carboxylic acid used for the copper complex having a carboxylic acid as a ligand, for example, a compound represented by the following formula (K) can be used.

[Chemical Formula 18]

(In the formula (K), R ¹ represents a monovalent organic group.)

In the formula (K), R ¹ represents a monovalent organic group. The monovalent organic group is not particularly limited, but is, for example, the same as the monovalent organic group in the above-mentioned formula (I).

(Inorganic fine particles)

The composition of the present invention may contain inorganic fine particles as another near infrared absorbing compound. The inorganic fine particles may be used alone, or two or more kinds may be used.

The inorganic fine particles are mainly particles that act to shield (absorb) infrared rays. The inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles because of their superior infrared ray shielding properties.

Examples of the inorganic fine particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO that is doped with Al) particles which may be doped with aluminum, fluorine doped tin dioxide Doped SnO ₂ ) particles or niobium-doped titanium dioxide (Nb doped TiO ₂ ) particles, silver (Ag) particles, gold (Au) particles, copper (Cu) And the like. In order to achieve both infrared light shielding property and photolithography property, a high transmittance of an exposure wavelength (365 to 405 nm) is preferable, and indium tin oxide (ITO) particles or antimony tin oxide (ATO) particles are preferable.

The shape of the inorganic fine particles is not particularly limited and may be a sheet, a wire, or a tube, irrespective of spherical or non-spherical shape.

As the inorganic fine particles, tungsten oxide-based compounds can be used, and more specifically, tungsten oxide-based compounds represented by the following general formula (composition formula) (I).

M _x W _y O _z ... (I)

M represents a metal, W represents tungsten, and O represents oxygen.

0.001? X / y?

2.2? Z / y? 3.0

As the metal of M, an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, But it is preferably an alkali metal and is preferably Rb or Cs, and it is preferably Cs, and more preferably, Cs is at least one selected from the group consisting of In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os and Bi. More preferable. The metal of M may be one kind or two kinds or more.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten oxide compound can be more reliably avoided.

When z / y is 2.2 or more, the chemical stability as a material can be further improved, and the infrared ray can be sufficiently shielded by having 3.0 or less.

The metal oxide is preferably tungsten oxide cesium.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _{0 . 33 WO 3, Rb 0.33 WO 3} , K 0. 33 WO 3, Ba 0. ₃₃ WO ₃ , And Cs _{0 . 33} WO ₃ or Rb _{0 . 33} WO ₃ , and Cs _{0 . 33} WO ₃ is more preferable.

The metal oxide is preferably fine particles. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. Since the average particle diameter is within this range, the metal oxide is less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be more surely obtained. From the viewpoint of avoiding light scattering, the smaller the average particle diameter is, the better, but the average particle diameter of the metal oxide is usually 1 nm or more for ease of handling at the time of production.

The tungsten oxide compound can be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Chemical Co., Ltd.

The content of the metal oxide is preferably 0.01 to 30 mass%, more preferably 0.1 to 20 mass%, and further preferably 1 to 10 mass% with respect to the total solid content of the composition containing the metal oxide .

<Solvent>

The solvent used in the present invention is not particularly limited and may be appropriately selected depending on the purpose so long as each component of the composition of the present invention can be uniformly dissolved or dispersed. Examples of the solvent include water-based solvents such as water and alcohols . In addition, the solvent used in the present invention may be an organic solvent, a ketone, an ether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and dimethylformamide, dimethylacetamide, dimethylsulfoxide , Sulfolane, and the like. These may be used alone, or two or more kinds may be used in combination.

Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in Japanese Laid-Open Patent Publication No. 2012-194534, paragraph 0136, the contents of which are incorporated herein by reference. Specific examples of the esters, ketones and ethers are those described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0497 (corresponding to United States Patent Application Publication No. 2012/0235099 [0609]), and acetic acid- n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether and ethylene glycol monobutyl ether acetate.

It is particularly preferable that the composition of the present invention contains water. Water is preferably contained in an amount of 40 to 95 mass% with respect to the composition of the present invention, and more preferably 50 to 85 mass% with respect to the composition of the present invention.

When the composition of the present invention contains a solvent other than water, it is preferably contained in a proportion of from 40 to 90% by mass with respect to the composition of the present invention. The solvent other than water may be one kind or two kinds or more.

<Curable compound>

The composition of the present invention may further contain a curable compound. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. In addition, a thermosetting compound or a photo-curing compound may be used, but a thermosetting composition is preferable because of a high reaction rate.

<< Compounds having polymerizable groups >>

The composition of the present invention may contain a compound having a polymerizable group (hereinafter sometimes referred to as a "polymerizable compound"). Such a group of compounds is widely known in the industrial field, and they can be used without any particular limitation in the present invention. These may be any one of chemical forms such as monomers, oligomers, prepolymers, polymers, and the like.

<< Polymerizable Monomers and Polymerizable Oligomers >>

The composition of the present invention is a composition comprising a monomer having a polymerizable group (a polymerizable monomer) or an oligomer having a polymerizable group (a polymerizable oligomer) (hereinafter, a polymerizable monomer or the like, May be included).

Examples of the polymerizable monomer and the like include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides, An ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As specific compounds of these, compounds described in paragraph [0095] to [0108] of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

The polymerizable monomer may be a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 under normal pressure, and may be a monofunctional (meth) acrylate, a bifunctional ) Acrylate, and trifunctional or more (meth) acrylate (e.g., (meth) acrylate having 3 to 6 functional groups).

Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate;

(Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane, and then (meth) acrylate.

As the polymerizable compound, ethyleneoxy-modified pentaerythritol tetraacrylate (NK Ester ATM-35E, Shin Nakamura Kagaku Co., Ltd., a commercial product), dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki (KAYARAD D-320 manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310, manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol tetraacrylate (Trade name, KAYARAD DPHA, manufactured by Nippon Kayaku K.K.) and their (meth) acryloyl groups are ethylene glycol, propylene glycol residues (manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa Can be used. These oligomer types can also be used. The compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 can also be used in the present invention.

Polymerizable monomers and the like include polymerizable monomers described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0477 (corresponding to United States Patent Application Publication No. 2012/0235099 [0585]), Is used. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (M-460, commercially available from Toagosei Co., Ltd.) can be used. Pentaerythritol tetraacrylate (Shin-Nakamura Kagaku Co., A-TMMT) and 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.) can also be used. These oligomer types can also be used.

For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group Can be used. Commercially available products include, for example, M-305, M-510, and M-520 of Aronix series as a polybasic acid-modified acrylic oligomer made by Toagosei Co.,

The acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is essential to prepare the polyfunctional monomers so that the total acid value of the polyfunctional monomer falls within the above range.

<< Polymer having polymerizable group in side chain >>

The second aspect of the composition of the present invention may be a mode in which the polymerizable compound includes a polymer having a polymerizable group in its side chain. Examples of the polymerizable group include an ethylenically unsaturated double bond group, an epoxy group and an oxetanyl group.

&Lt; Compound having an epoxy group or oxetanyl group &gt;

The third aspect of the present invention may be a mode in which a compound having an epoxy group or an oxetanyl group is contained as the polymerizable compound. Specific examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in the side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, Novolak type epoxy resins, cresol novolak type epoxy resins, and aliphatic epoxy resins. Also included are monofunctional or polyfunctional glycidyl ether compounds.

These compounds may be commercially available products or may be obtained by introducing an epoxy group into the side chain of the polymer. As a commercial product, for example, Japanese Laid-Open Patent Publication No. 2012-155288, paragraph 0191 and the like can be taken into consideration, and these contents are incorporated herein by reference.

As a commercial product, polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L and EX-850L (manufactured by Nagase ChemteX Corporation) . These are low-salt small articles, but EX-212, EX-214, EX-216, EX-321, EX-850 and the like can be used in the same manner.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S, and the like.

Examples of commercially available phenol novolac epoxy resins include JER-157S65, JER-152, JER-154 and JER-157S70 (manufactured by Mitsubishi Kagaku Co., Ltd.).

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having at least two oxetane groups in the molecule include Aromatic oxetane OXT-121, OXT-221, OX-SQ and PNOX Manufactured by Toagosei Co., Ltd.) can be used.

In the case of synthesizing by introduction into the side chain of the polymer, the introduction reaction is carried out, for example, by using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride , Pyridine, triphenylphosphine or the like as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several hours. The introduction amount of the alicyclic epoxy unsaturated compound can be controlled so that the acid value of the obtained polymer is in the range satisfying 5 to 200 KOH · mg / g. The weight average molecular weight may be in the range of 500 to 5000000, more preferably 1000 to 500000.

As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether can also be used. For example, Japanese Patent Application Laid-Open No. 2009-265518, paragraph 0045, and the like can be taken into consideration, and these contents are incorporated herein by reference.

In the present invention, it is preferable to include a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetane group. This makes it possible to improve film formability (suppression of cracking and warping) and moisture resistance when the film is formed into a cured film. Specifically, a polymer having the following repeating unit can be mentioned. As the polymer having the following repeating unit, a polymer having an epoxy group is preferable.

[Chemical Formula 19]

<< Compounds having a partial structure represented by the formula (1) >>

The curable compound used in the present invention preferably has a partial structure represented by the following formula (1), and the curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

[Chemical Formula 20]

(In the formula (1), R ¹ represents a hydrogen atom or an organic group.)

By containing such a compound, when the near infrared absorbing composition of the present invention is used as a cured film, the near infrared ray shielding property can be further improved and the moisture resistance can be further improved.

In the formula (1), R ¹ represents a hydrogen atom or an organic group. The organic group is preferably a hydrocarbon group, specifically, an alkyl group or an aryl group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination of these groups and a divalent linking group .

Specific examples of such an organic group include -OR ', -SR', or a group of these groups and - (CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, -O-, CO-, -COO-, and -NH-. Here, R 'represents a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms (preferably a straight chain having 1 to 7 carbon atoms, a branched or cyclic alkyl group having 3 to 7 carbon atoms ), An aryl group having 6 to 10 carbon atoms, or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms.

In formula (1), R ¹ and C may be bonded to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is a nitrogen atom in formula (1). The heterocyclic structure is preferably a 5- or 6-membered ring structure, and more preferably a 5-membered ring structure. The heterocyclic structure may be a condensed ring, but monocyclic ring is preferred.

Specific examples of the preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, -OR '(R' is a straight chain alkyl group having 1 to 5 carbon atoms) and - (CH ₂ ) _m - (Preferably an integer of 1 to 5), and a group formed by combining R ¹ and C in formula (1) to form a heterocyclic structure (preferably a 5-membered ring structure).

The compound having a partial structure represented by the formula (1) may be represented by (a main chain structure of the polymer - a partial structure of formula (1) - R ¹ ), or a compound represented by the following formula desirable. Here, A is a straight chain, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, having 1 to 10 carbon atoms. B represents a group consisting of a partial structure of the formula (1) and a polymerizable group, - (CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5) to be.

The compound having a partial structure represented by the formula (1) preferably has a structure represented by any one of the following formulas (1-1) to (1-5).

[Chemical Formula 21]

(In formula (1-1) of, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ and R ⁶ represents a hydrogen atom or an organic each independently formula (1-2) of, R ⁷ is a hydrogen atom or a methyl group represents the equation (1-3) of the, L ¹ represents a divalent connecting group, R ⁸ represents a hydrogen atom or an organic group. Eq. (1-4) of the, L ² and L ³ each independently represents a divalent linking group (1-5), L ⁴ represents a divalent linking group, R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or an organic group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an organic group. .

In the formula (1-1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. The organic group agrees with R ¹ in formula (1), and the preferable range is also the same.

In formulas (1-3) to (1-5), L ¹ to L ⁴ represent a divalent linking group. As the divalent linking group, at least one of - (CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, -O-, -CO-, -COO- and -NH- , And more preferably - (CH ₂ ) _m - (m is an integer of 1 to 8).

In formulas (1-3) to (1-5), R ⁸ to R ¹⁴ each independently represent a hydrogen atom or an organic group. The organic group is preferably a hydrocarbon group, specifically an alkyl group or an alkenyl group.

The alkyl group may be substituted. The alkyl group may be any of chain, branched, and cyclic, but is preferably straight-chain or cyclic. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

The alkenyl group may be substituted. As the alkenyl group, an alkenyl group having 1 to 10 carbon atoms is preferable, an alkenyl group having 1 to 4 carbon atoms is more preferable, and a vinyl group is particularly preferable.

Examples of the substituent include a polymerizable group, a halogen atom, an alkyl group, a carboxylic acid ester group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloyloxy group, an ether group, a sulfonyl group, a sulfide group, An acyl group, a hydroxyl group, a carboxyl group and the like. Among these substituents, a polymerizable group (e.g., a vinyl group, a (meth) acryloyloxy group, a (meth) acryloyl group, an epoxy group, an aziridinyl group, etc.) is preferable and a vinyl group is more preferable.

The compound having a partial structure represented by the formula (1) may be a monomer or a polymer, but is preferably a polymer. That is, the compound having a partial structure represented by the formula (1) is preferably a compound represented by the formula (1-1) or (1-2).

When the compound having a partial structure represented by the formula (1) is a polymer, it is preferable that the side chain of the polymer contains the partial structure.

The molecular weight of the compound having the partial structure represented by the formula (1) is preferably 50 to 1000000, more preferably 500 to 500000. By using such a molecular weight, the effect of the present invention can be achieved more effectively.

The content of the compound having a partial structure represented by the formula (1) is preferably 5 to 80% by mass, more preferably 10 to 60% by mass in the composition of the present invention.

Specific examples of the compound having a partial structure represented by the formula (1) include a compound having the following structure or the following exemplified compounds, but are not limited thereto. In the present invention, it is particularly preferable that the compound having a partial structure represented by the formula (1) is a polyacrylamide.

[Chemical Formula 22]

Specific examples of the compound having a partial structure represented by the formula (1) include water-soluble polymers. Preferred examples of the main chain structure include polyvinylpyrrolidone, poly (meth) acrylamide, polyamide, polyvinylpyrrolidone , Polyurethane, and polyurea. The water-soluble polymer may be a copolymer, and the copolymer may be a random copolymer.

As the polyvinylpyrrolidone, a trade name KW-30 (manufactured by Nippon Shokubai Co., Ltd.) may be used.

Examples of the poly (meth) acrylamide include polymers and copolymers of (meth) acrylamide. Specific examples of acrylamide include acrylamide, N-methylacrylamide, N-ethyl acrylamide, N-propylacrylamide, N-butyl acrylamide, N-benzyl acrylamide, N-hydroxyethyl acrylamide, (Phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N (hydroxyphenyl) acrylamide, N- , N-dimethyl acrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like. The corresponding methacrylamides can also be used as such.

The water-soluble polyamide resin may particularly be a compound obtained by copolymerizing a polyamide resin with a hydrophilic compound. Derivatives of the water-soluble polyamide resin include derivatives of a water-soluble polyamide resin such as water-soluble polyamide resin as a raw material and a compound obtained by substituting hydrogen (- atom of the --CONH-) with methoxymethyl group (CH ₂ OCH ₃ ) Refers to a compound in which the atom in the amide resin molecule is substituted or the structure of the amide bond is changed by an addition reaction.

As the polyamide resin, there may be mentioned, for example, so-called "n-nylon" synthesized by polymerization of ω-amino acid or so-called "n, m-nylon" synthesized by copolymerization of diamine and dicarboxylic acid. Among them, a copolymer of a diamine and a dicarboxylic acid is preferable from the viewpoint of imparting hydrophilicity, and a reaction product of? -Caprolactam and a dicarboxylic acid is more preferable.

Examples of the hydrophilic compound include hydrophilic nitrogen-containing cyclic compounds and polyalkyleneglycols.

Here, the hydrophilic nitrogen ring cyclic compound is a compound having a tertiary amine component in the side chain or the main chain, and examples thereof include aminoethylpiperazine, bisaminopropylpiperazine,? -Dimethylamino? Caprolactam, and the like. have.

On the other hand, in the compound in which the polyamide resin and the hydrophilic compound are copolymerized, at least one selected from the group consisting of a hydrophilic cyclic nitrogen compound and a polyalkyleneglycol is copolymerized with the main chain of the polyamide resin, The hydrogen bonding ability of the amide bond portion of the resin is larger than that of N-methoxymethylated nylon.

Among the compounds in which a polyamide resin and a hydrophilic compound are copolymerized, 1) a reaction product of? -Caprolactam and a hydrophilic nitrogen cyclic compound and a dicarboxylic acid, and 2) a reaction product of? -Caprolactam and a polyalkylene glycol and a dicarboxylic acid Reaction products are preferred.

These are commercially available under the trademark "AQ nylon ", for example, from Toray Fine Tech Co., Ltd. The reaction product of? -caprolactam and a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid is available as AQ Nylon A-90 manufactured by Toray Fine Chemicals Co., Ltd., and? -caprolactam, polyalkyleneglycol and dicarboxylic acid Is available as AQ Nylon P-70 manufactured by Toray Fine Chemicals Co., Ltd. AQ nylon A-90, P-70, P-95, and T-70 (manufactured by Toray Industries, Inc.).

The molar ratio of the repeating unit having a partial structure and the repeating unit having an epoxy group represented by the above-mentioned formula (1) is preferably 10/90 to 90/10, more preferably 30/70 to 70/30 desirable. The weight average molecular weight of the copolymer is preferably 3,000 to 1,000,000, more preferably 5,000 to 200,000.

Details of the structure, the use of the polymerizable compound, whether it is used alone or in combination with the polymerizable compound, and the like can be arbitrarily set in accordance with the final performance design of the near infrared absorbing composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. From the viewpoint of enhancing the strength of the near-IR blocking filter, it is preferable to use a trifunctional or higher functional group, and a combination of other functional groups and other polymerizable groups (for example, acrylate ester, methacrylate ester, styrene group compound, vinyl ether group compound) A method of adjusting both the sensitivity and the intensity is also effective. In addition, regarding the compatibility and dispersibility with other components (for example, metal oxides, pigments, polymerization initiators) contained in the near-infrared absorbing composition, selection and use of polymerizable compounds are important factors. For example, May be used, or the compatibility may be improved by combining two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

The amount of the polymerizable compound to be added in the composition of the present invention is in the range of 1 to 50 mass%, more preferably 1 to 30 mass%, and particularly preferably 1 to 10 mass% with respect to the total solid content excluding the solvent .

When a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, the amount of the polymer is preferably 10 to 75% by mass, more preferably 20 to 65% by mass, particularly preferably 20 to 80% by mass relative to the total solid content of the composition of the present invention, By mass to 20% by mass to 60% by mass.

The polymerizable compound may be a single kind or two or more kinds, and when two or more kinds are used, the total amount is in the above range.

&Lt; Binder polymer &

In the present invention, for the purpose of improving the film properties, etc., a binder polymer may be further included if necessary. As the binder polymer, an alkali-soluble resin can be used.

As the alkali-soluble resin, mention may be made of the description after Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to United States Patent Application Publication No. 2012/0235099 [0685] to [0700]), Which is incorporated herein by reference.

The content of the binder polymer in the present invention may be 80% by mass or less, 50% by mass or less, and 30% by mass or less, based on the total solid content of the composition.

<Surfactant>

The composition of the present invention may contain a surfactant. Only one surfactant may be used, or two or more surfactants may be combined. The amount of the surfactant to be added may be from 0.0001 to 2 mass%, preferably from 0.005 to 1.0 mass%, and from 0.01 to 0.1 mass%, based on the solid content of the composition of the present invention.

As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the composition of the present invention contains at least any one of a fluorine-based surfactant and a silicone-based surfactant, the liquid property (particularly, fluidity) when the composition is prepared as a coating liquid is further improved, The liquid-storing property can be further improved.

That is, when a film is formed using a coating liquid to which a composition containing at least one of a fluorine-based surfactant and a silicone-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, So that the coating property to the surface to be coated is improved. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine-based surfactant may be, for example, 3 to 40% by mass.

Examples of the fluorine-based surfactant include Megapac F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F479, copper F482, copper F554 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, S-141, and S-141 (all manufactured by DIC Corporation) (Above), SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and K- (Manufactured by OMNOVA), EF Top EF301, EF303, EF351 and EF352 (manufactured by Zemko Co., Ltd.), PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA).

As the fluorine-based surfactant, a polymer having a fluoroaliphatic group can be used. Examples of the polymer having a fluoroaliphatic group include a fluoroaliphatic group having a fluoroaliphatic group and a fluoroaliphatic group such as a fluoroaliphatic group produced according to the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method) Based surfactant.

Here, the "telomerization method" means a method of synthesizing a compound having one or two active groups in the molecule by polymerizing a substance having a low molecular weight. Further, the "oligomerization method" means a method of converting a monomer or a mixture of monomers into an oligomer.

Examples of the fluoroaliphatic group in the present invention include -CF ₃ group, -C ₂ F ₅ group, -C ₃ F ₇ group, -C ₄ F ₉ group, -C ₅ F ₁₁ group, -C ₆ F ₁₃ group, -C ₇ F ₁₅ group, -C ₈ F ₁₇ group, C ₉ F ₁₉ group and C ₁₀ F ₂₁ group, and from the viewpoint of compatibility and application property, -C ₂ F ₅ group, -C ₃ F ₇ group, -C ₄ F ₉ group, -C ₅ F ₁₁ group, -C ₆ F ₁₃ group, -C ₇ F ₁₅ group and -C ₈ F ₁₇ group can be used.

The fluoroaliphatic compound in the present invention can be synthesized according to the method described in JP-A-2002-90991.

Examples of the polymer having a fluoroaliphatic group in the present invention include a fluoroaliphatic group-containing monomer and a (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate May be used. The copolymer may be irregularly distributed or may be subjected to block copolymerization. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group and a poly (oxybutylene) group. Block linking group) or poly (block linking group of oxyethylene and oxypropylene) group, or may be a unit having other chain alkylene in the same chain. Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) may be a monomer having two or more different fluoroaliphatic groups, (Poly (oxyalkylene)) acrylate (or methacrylate) or the like may be copolymerized at the same time.

As a commercially available surfactant containing a polymer having a fluoroaliphatic group in the present invention, for example, Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0552 (corresponding to United States Patent Application Publication No. 2012/0235099 [0678]), And the like, the content of which is incorporated herein by reference. (Methacrylate) having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate (or methacrylate (meth) acrylate having a C ₆ F ₁₃ group) ) And (poly (oxypropylene)) acrylate (or methacrylate), copolymers of acrylate (or methacrylate) having C ₈ F ₁₇ groups with (poly (oxyalkylene) (Meth) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group, Rate) may be used.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamine, glycerin fatty acid esters , Oxyethylene oxypropylene block copolymer, acetylene glycol surfactant, and acetylene-based polyoxyethylene oxide. These may be used alone or in combination of two or more.

Concrete product names include Surfynol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT- DF-75, DF-110, DF-210, GA, OP-340, PSA-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF- A-B, AK-02, CT-151W, and DYNOL 604 (all manufactured by Nisshin Chemical Industries, Ltd. and AirProducts & Chemicals), PSA-216, PSA-216, PSA-336, SE, SE- PD-001, PD-002W, PD-003, PD-004, EXP, SP, STG, Y, 32W, E1004, E1010, 4001, EXP. 4036, EXP. E51, E40, E60, E81, E100, and E200 (all trade names, Kawaken Co., (Manufactured by Fine Chemical Co., Ltd.). Of these, Olfin E1010 is suitable.

Specific examples of the nonionic surfactant include nonionic surfactants described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraph 0553 (corresponding to United States Patent Application Publication No. 2012/0235099 [0679]), etc. , The contents of which are incorporated herein by reference.

Specific examples of the cationic surfactant include cationic surfactants described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0554 (corresponding to United States Patent Application Publication No. 2012/0235099 [0680]), Which is incorporated herein by reference.

Specific examples of the anionic surfactant include W004, W005 and W017 (manufactured by YUHO Co., Ltd.).

Examples of the silicone surfactants include silicone surfactants described in Japanese Patent Laid-Open Publication No. 2012-208494, paragraph 0556 (corresponding to United States Patent Application Publication No. 2012/0235099 [0682]), . "TSF-400" manufactured by Momentive Performance Materials Co., Ltd., "TORAY Silicone SF8410", "Dong SF8427", "SH8400", "ST80PA", "ST83PA", "ST86PA" manufactured by Toray Dow Corning Co., TSF-401, TSF-410, TSF-4446, KP321, KP323, KP324, and KP340 manufactured by Shin-Etsu Silicones.

<Polymerization Initiator>

The composition of the present invention may contain a polymerization initiator. The polymerization initiator may be used singly or in combination of two or more, and in the case of two or more types, the total amount is in the above range. For example, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 15% by mass, based on the solid content of the composition of the present invention.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either or both of light and heat, and may be appropriately selected depending on the purpose, but it is preferably a photopolymerizable compound. In the case of initiating polymerization by light, it is preferable to have photosensitivity to visible light from the ultraviolet region.

When heat polymerization is initiated, a polymerization initiator which decomposes at 150 to 250 캜 is preferable.

The polymerization initiator usable in the present invention is preferably a compound having at least an aromatic group, and examples thereof include acylphosphine compounds, acetophenone compounds,? -Amino ketone compounds, benzophenone compounds, benzoin ether compounds, An azo compound, an organic peroxide, a diazonium compound, an iodonium compound, a sulfonium compound, an azinium compound, a benzoin compound, a benzoin compound, An onium salt compound such as an ether-based compound, a ketal derivative compound, and a metallocene compound, an organic boron salt compound, and a disulfone compound.

From the viewpoint of sensitivity, oxime compounds, acetophenone compounds,? -Amino ketone compounds, trihalomethyl compounds, hexaarylbaimidazole compounds and thiol compounds are preferable.

Specific examples of the acetophenone compound, the trihalomethyl compound, the hexaarylbaimidazole compound and the oxime compound are described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraphs 0506 to 0510 (corresponding US Patent Application Publication No. 2012/0235099 [0622] to [0628]), etc., which are incorporated herein by reference.

As the photopolymerization initiator, a compound selected from the group consisting of oxime compounds, acetophenone compounds and acylphosphine compounds is more preferable. More specifically, for example, an aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969, an acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898, a oxime-based initiator described above, , Compounds described in Japanese Patent Application Laid-Open No. 2001-233842 may also be used.

As the oxime compounds, commercially available IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, all manufactured by BASF Japan) can be used. As the acylphosphine-based initiator, commercial products IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF Japan) can be used.

<Other ingredients>

To the composition of the present invention, other components may be appropriately selected and used depending on the purpose, in addition to the essential components and additives described above, so long as the effect of the present invention is not impaired.

Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor and a plasticizer. A conductive agent, a filler, a defoaming agent, a flame retardant, a leveling agent, a release promoter, an antioxidant, a flavor, a surface tension adjuster, a chain transfer agent, etc. may be used in combination.

By suitably containing these components, it is possible to adjust properties such as stability and film physical properties of the objective near-infrared absorbing filter.

These components are described, for example, in Japanese Patent Laid-Open Publication No. 2012-003225, paragraphs 0183 and 2013 (corresponding to [0237] of U.S. Patent Application Publication No. 2013/0034812), Japanese Patent Application Publication No. 2008-250074 0101 to 0102, paragraph numbers 0103 to 0104, and paragraph numbers 0107 to 0109 can be taken into consideration, and these contents are incorporated herein by reference.

Since the composition of the present invention can be in the form of a liquid, for example, the composition of the present invention can be directly applied and dried, thereby making it possible to easily manufacture a near-infrared cutoff filter. In addition, The manufacturing aptitude can be improved.

The near infrared ray shielding filter of the present invention preferably has a rate of change of the absorbance ratio determined by the following equation before and after heating at 200 DEG C for 5 minutes, preferably 7% or less, more preferably 5% or less, More preferable.

[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]

Here, the term "absorbance ratio" refers to (the maximum absorbance at a wavelength of 700 to 1400 nm / the minimum absorbance at a wavelength of 400 to 700 nm).

The near infrared ray shielding filter of the present invention preferably has a change ratio of the absorbance ratio determined by the following equation before and after being left under high temperature and high humidity of 85 캜 / 95% RH for 3 hours, preferably 7% or less, more preferably 5% , And more preferably 2% or less.

[(Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test]

Here, the term "absorbance ratio" refers to (the maximum absorbance at a wavelength of 700 to 1400 nm / the minimum absorbance at a wavelength of 400 to 700 nm).

The thickness of the near infrared ray shielding filter of the present invention is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably 1 to 500 μm, more preferably 1 to 300 μm, and particularly preferably 1 to 200 μm. In the present invention, even in the case of such a thin film, high near infrared ray shielding property can be maintained.

The use of the near infrared ray absorbent composition of the present invention is not particularly limited, but the use of the near infrared ray absorbing composition for the near infrared ray shielding filter (for example, for a near-infrared ray filter for a wafer level lens) on the light receiving side of the solid- For the near-infrared ray blocking filter on the back side (the side opposite to the light receiving side) of the solid-state imaging element substrate, and is preferably for the light-shielding film on the light receiving side of the solid-state imaging element substrate. In particular, it is preferable that the near infrared absorbing composition of the present invention is directly applied on an image sensor for a solid-state imaging element to form a coating film.

In particular, it is preferable that the near infrared ray absorbing composition of the present invention comprises a copper compound and a near infrared ray shielding filter containing the structure of formula (1) and having a film thickness of 200 μm or less and a visible light transmittance of 90% or more.

The viscosity of the near infrared absorbing composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s in the case of forming the infrared ray blocking layer by coating s or less, more preferably in the range of 100 mPa · s or more and 1500 mPa · s or less.

When the near infrared absorbing composition of the present invention is used for a near infrared ray shielding filter on the light receiving side of the solid-state imaging element substrate, when forming the infrared ray blocking layer by coating, from 10 mPa · s to 3,000 mPa · s s or less, more preferably 500 mPa · s or more and 1,500 mPa · s or less, and most preferably 700 mPa · s or more and 1,400 mPa · s or less.

The total solid content of the near infrared absorbing composition of the present invention varies depending on the application method, but is preferably 1 to 50 mass%, more preferably 1 to 30 mass%, and more preferably 10 to 30 mass% desirable.

The present invention may be a laminate having a near infrared ray blocking layer and a dielectric multilayer film obtained by curing the near infrared absorbing composition. For example, there are embodiments in which (i) a transparent support, a near-infrared ray blocking layer, and a dielectric multilayer film are provided in this order, (ii) a near-infrared ray blocking layer, a transparent support, and a dielectric multilayer film are provided in this order. The transparent support may be a glass substrate or a transparent resin substrate.

The dielectric multilayer film is a film having an ability to reflect and / or absorb near-infrared rays.

As a material of the dielectric multilayer film, for example, a ceramic can be used. Alternatively, the noble metal film having absorption in the near infrared region may be used in consideration of the thickness and the number of layers so as not to affect the transmittance of the visible light of the near-IR cut filter.

Specifically, as the dielectric multilayer film, a structure in which a high refractive index material layer and a low refractive index material layer are alternately laminated can be suitably used.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected.

Examples of the material include titanium oxide (titania), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, Titanium, tin oxide and / or cerium oxide in a small amount. Of these, titanium oxide (titania) is preferable.

As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of usually 1.2 to 1.6 is selected.

Examples of the material include silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum sodium hexafluoride. Of these, silica is preferable.

The thicknesses of the respective layers of the high refractive index material layer and the low refractive index material layer are generally 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (nxd) of the refractive index (n) and the film thickness (d) greatly differs from the optical film thickness calculated by? / 4, It tends to be difficult to control blocking and transmission of a specific wavelength.

The number of laminated layers in the dielectric multilayer film is preferably 5 to 50 layers, and more preferably 10 to 45 layers.

In addition, the present invention relates to a method for manufacturing a solid-state imaging element substrate having a step of forming a film by applying (preferably applying or printing, and more preferably, applying an applicator) the near infrared absorbing composition of the present invention on a light receiving side of a solid- , And a manufacturing method of a near-infrared cut filter. The film thickness, the lamination structure, and the like can be appropriately selected depending on the purpose.

The support may be a transparent substrate made of glass or the like, a solid-state imaging element substrate, or another substrate provided on the light-receiving side of the solid-state imaging element substrate (for example, a glass substrate 30 described later) Or a planarization layer or the like provided on the light receiving side.

The method of applying the near infrared absorbing composition (coating liquid) on a support can be carried out by using, for example, a spin coater, a slit spin coater, a slit coater, a screen printing, an applicator coating or the like.

The drying condition of the coating film is usually from 60 to 200 DEG C for about 30 seconds to 15 minutes, though it depends on the components, the type of solvent, and the usage ratio.

The method for forming the near infrared ray shielding filter using the near infrared absorbing composition of the present invention may include other steps. The other processes are not particularly limited and can be appropriately selected according to the purpose. For example, the surface treatment process of the substrate, the preheating process (prebake process), the curing process process, the postheating process (postbake process) .

&Lt; Preheating process & Post-heating process &gt;

The heating temperature in the preheating step and the post-heating step is usually 80 to 200 占 폚, preferably 90 to 180 占 폚.

The heating time in the preheating step and the post-heating step is usually 30 seconds to 400 seconds, preferably 60 seconds to 300 seconds.

<Curing Treatment Step>

The curing treatment step is a step of performing a curing treatment for the film formed as necessary, and by performing this treatment, the mechanical strength of the near-infrared blocking filter is improved.

The curing treatment step is not particularly limited and can be appropriately selected according to the purpose. For example, the whole surface exposure treatment, the whole surface heating treatment and the like are suitably used. Here, in the present invention, the term "exposure" is used not only to light of various wavelengths but also to include irradiation with radiation such as electron beams and X-rays.

The exposure is preferably performed by irradiation with radiation, and ultraviolet rays or visible rays such as electron beam, KrF, ArF, g line, h line, i line and the like are preferably used as the radiation usable in exposure. Preferably, KrF, g line, h line, and i line are preferred.

Examples of the exposure method include stepper exposure and exposure using a high-pressure mercury lamp.

Exposure dose, and 5 ~ 3000mJ / cm ² are preferred and more preferably ^{10 ~ 2000mJ / cm 2, 50} ~ 1000mJ / cm 2 is particularly preferred.

As a method of the entire surface exposure treatment, for example, there is a method of exposing the entire surface of the formed film. In the case where the near infrared absorbing composition contains a polymerizable compound, the curing of the polymerization component in the film formed of the composition is promoted by the entire surface exposure, and the curing of the film progresses further, thereby improving the mechanical strength and durability.

The apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected according to the purpose. For example, a UV exposure apparatus such as an ultra-high-pressure mercury lamp is suitably used.

As a method of heating the entire surface, there is a method of heating the entire surface of the formed film. By heating the entire surface, the film strength of the pattern can be increased.

The heating temperature in the whole surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 250 ° C. When the heating temperature is 120 占 폚 or higher, the film strength is improved by the heat treatment. When the heating temperature is 250 占 폚 or lower, decomposition of the components in the film occurs, thereby preventing the film quality from becoming fragile.

The heating time for heating the entire surface is preferably 3 minutes to 180 minutes, more preferably 5 minutes to 120 minutes.

The apparatus for heating the entire surface is not particularly limited and may be appropriately selected from known apparatuses according to the purpose, and examples thereof include a dry oven, a hot plate, and an IR heater.

The present invention also relates to a camera module having a solid-state imaging element substrate and a near infrared ray blocking filter disposed on a light receiving side of the solid-state imaging element substrate, wherein the near infrared ray blocking filter is a near-infrared blocking filter of the present invention .

Hereinafter, a camera module according to an embodiment of the present invention will be described with reference to Figs. 3 and 4. However, the present invention is not limited to the following specific examples.

3 and 4, common reference numerals are given to common parts.

Quot; lower ", " lower ", and "lower side" refer to the side farther from the silicon substrate 10 than to the silicon substrate 10, To the nearest side.

3 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image pickup device.

The camera module 200 shown in Fig. 3 is connected to a circuit board 70, which is a mounting board, via a solder ball 60, which is a connecting member.

Specifically, the camera module 200 includes a solid-state imaging element substrate 100 having an imaging element portion on a first main surface of a silicon substrate, and a plurality of pixel electrodes (not shown) provided on the first main surface side A planarization layer (not shown in FIG. 3), a near-infrared cut filter 42 provided on the planarization layer, a lens holder 50 disposed above the near-infrared cut filter 42 and having an image pickup lens 40 in the inner space, And a light shielding and electronic shield 44 arranged so as to surround the periphery of the solid-state imaging element substrate 100 and the glass substrate 30. Further, a glass substrate 30 (light-transmitting substrate) may be provided on the planarizing layer. Each member is adhered by an adhesive 45.

The present invention is a method of manufacturing a camera module having a solid-state imaging element substrate (100) and a near-infrared cutoff filter (42) disposed on the light receiving side of the solid-state imaging element substrate, Infrared absorbing composition according to the present invention. In the camera module according to the present embodiment, the near infrared ray blocking filter 42 can be formed by forming a film by applying the near infrared ray absorbing composition of the present invention on a planarizing layer, for example. The method of applying the near-infrared cutoff filter is as described above.

In the camera module 200, incident light hν from the outside sequentially passes through the imaging lens 40, the near-infrared ray blocking filter 42, the glass substrate 30, and the flattening layer, And reaches the element portion.

The camera module 200 is provided with a near infrared ray cut filter directly on the planarization layer. However, the planarization layer may be omitted and a near infrared ray cut filter may be provided directly on the microlens. A near infrared ray cut filter Or a glass substrate 30 provided with a near-infrared cutoff filter may be applied.

4 is an enlarged cross-sectional view of the solid-state imaging element substrate 100 in Fig.

The solid-state imaging element substrate 100 includes an imaging element 12, an interlayer insulating film 13, a base layer 14, a color filter 15, an overcoat 16 ), And a microlens 17 in this order. The red color filter 15R, the green color filter 15G and the blue color filter 15B (hereinafter collectively referred to as "color filter 15" ) And the microlenses 17 are arranged, respectively. A light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and an element surface electrode (not shown) are formed on a second main surface of the silicon substrate 10 opposite to the first main surface. 27). Each member is bonded by an adhesive 20.

On the microlens 17, a planarization layer 46 and a near-IR cut filter 42 are provided. The near infrared ray blocking filter 42 may be provided on the microlens 17, between the base layer 14 and the color filter 15 or between the color filter 15 and the overcoat 16 may be provided with a near-infrared cutoff filter. Particularly, it is preferable that it is provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. It is possible to simplify the step of forming the near-IR blocking filter and to sufficiently block the unnecessary near-infrared rays to the microlens, so that the near-IR blocking property can be further improved.

As for the solid-state imaging element substrate 100, the following description of the solid-state imaging element substrate 100 after paragraph 0245 (corresponding to [0407] of U.S. Patent Application Publication No. 2012/068292) , The contents of which are incorporated herein by reference.

As described above, one embodiment of the camera module has been described with reference to Figs. 3 and 4. However, the above embodiment is not limited to the configurations of Figs. 3 and 4. Fig.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

<Synthesis Example>

&Lt; Synthesis of Polymer (A1) >

&Lt; Synthesis of Polymer A-1 &gt;

5.0 g of polyethersulfone (Ultrason E6020P manufactured by BASF) was dissolved in 46 g of sulfuric acid, and 16.83 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. After reaction at room temperature for 48 hours, the reaction solution was added dropwise to 1 L of a mixed solution of hexane / ethyl acetate (1/1) cooled with ice water. The supernatant was removed, and the obtained precipitate was dissolved in methanol. The resulting solution was added dropwise to 0.5 liter of ethyl acetate, and the resulting precipitate was recovered by filtration. The resulting solid was dried under reduced pressure to obtain 4.9 g of polymer A-1. The sulfonic acid group content (meq / g) in the polymer was calculated by neutralization titration. The weight average molecular weight (Mw) was measured by gel permeation chromatography.

(23)

<< Synthesis of Polymer A-2 >>

Polymer A-2 was obtained in the same manner as in the synthesis of Polymer A-1, except that the amount of chlorosulfonic acid was changed to 25.1 g and the reaction temperature and time were changed to 7 hours at 70 캜.

&Lt; EMI ID =

<< Synthesis of Polymer A-3 >>

Polymer A-3 was obtained in the same manner as in the synthesis of the polymer A-1 except that chlorosulfonic acid was changed to 14.4 g of 30% fuming sulfuric acid and the reaction time was changed to 8 hours.

(25)

<< Synthesis of polymer A-4 >>

8.0 g of polysulfone (manufactured by Aldrich) was dissolved in 92.0 g of chloroform, and 8.43 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. Upon reaction at room temperature for 1 hour, a solid precipitated. The supernatant was removed, and the resulting solid was washed with chloroform and then dissolved in methanol. This solution was added dropwise to 0.5 liter of ethyl acetate, and the resulting precipitate was collected by filtration. The resulting solid was dried under reduced pressure to obtain 8.3 g of polymer A-4.

(26)

&Lt; Synthesis of polymer A-5 &gt;

In a three-necked flask equipped with a Dean Stark tube, 3.42 g of hexafluorobisphenol A, 5.00 g of dipotassium sulfone-4,4'-dichloro-3,3'-disulfonic acid disodium, 1.69 g of potassium carbonate, And 25 g of N-methylpyrrolidone were added, and the mixture was refluxed under a nitrogen stream for 4 hours. After toluene in the system was removed, the temperature was raised to 180 캜 and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama-rohto funnel on the whole surface of celite, and the filtrate was added dropwise to 300 ml of a saturated aqueous solution of sodium chloride. The resulting precipitate was filtered, dissolved in methanol, and then added dropwise in 500 ml of acetone. The obtained precipitate was filtered and dissolved in methanol, and then the salt was changed to a proton type by Amberlyst 15 (hydrogen form) (manufactured by aldrich) to obtain 6.4 g of polymer A-5.

(27)

<< Synthesis of polymer A-6 >>

3.9 g of polymer A-6 was obtained in the same manner as in the synthesis of polymer A-5, except that 3.42 g of hexafluorobiphenol A was changed to 1.12 g of hydroquinone.

(28)

<< Synthesis of polymer A-7 >>

In a three-necked flask equipped with a Dean Stark tube, 4.66 g of diphenol acid, 8.00 g of disodium diphenylsulfone-4,4'-dichloro-3,3'-disulfonate, 2.48 g of potassium carbonate, 10 g of toluene, 25 g of N-methylpyrrolidone was added, and the mixture was refluxed for 4 hours under a nitrogen stream. After toluene in the system was removed, the temperature was raised to 180 캜 and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a celite pad on the entire surface of celite, and the filtrate was added dropwise to 300 ml of a saturated aqueous solution of sodium chloride. The resulting precipitate was filtered, dissolved in methanol, and then added dropwise in 500 ml of acetone. The resulting precipitate was filtered and dried under reduced pressure.

The dried polymer was dissolved in 73.6 g of sulfuric acid, and 4.56 g of chlorosulfonic acid was added dropwise. After reaction at room temperature for 6 hours, the reaction solution was added dropwise to 1.5 liters of a mixed solution of hexane / ethyl acetate (1/1) cooled with ice water. The supernatant was removed, and the obtained precipitate was dissolved in methanol. The resulting solution was added dropwise to 0.5 liter of ethyl acetate, and the resulting precipitate was recovered by filtration. The resulting solid was dried under reduced pressure to obtain 7.5 g of polymer A-7.

[Chemical Formula 29]

<< Synthesis of Polymer A-8 >>

In a three-necked flask equipped with a Dean Stark tube, 3.53 g of 4,4'-biphenol, 8.00 g of disodium benzophenone-4,4'-difluoro-3,3'-disulfonic acid, 3.14 g , 10 g of toluene and 30 g of dimethyl sulfoxide were added, and the mixture was refluxed for 4 hours under a nitrogen stream. After toluene in the system was removed, the temperature was raised to 170 캜 and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered with a celite pad over the entire surface, and the filtrate was added dropwise into 500 ml of a saturated aqueous solution of sodium chloride. The resulting precipitate was filtered, dissolved in methanol, and then added dropwise in 800 ml of acetone. The resulting precipitate was filtered and dissolved in methanol, and then the product was subjected to salt exchange with a proton type by Amberlyst 15 (hydrogen form) (manufactured by aldrich) to obtain 7.2 g of polymer A-8.

(30)

&Lt; Synthesis of polymer A-9 &gt;

J. Membr. Sci. 229, 2004, 95 to obtain a polymer A-9 by sulphating a polyetheretherketone.

(31)

<< Synthesis of polymer A-10 >>

Chinese J. Polym. Sci. 20, No. 1, 2002, 53-, the polymer A-10 was obtained by sulfating the polyphenylene oxide.

(32)

<< Synthesis of polymer A-11 >>

Polymer A-11 was obtained in accordance with the method described in Example 2 of Japanese Patent Publication No. 2008-533225.

(33)

&Lt; Synthesis of Polymer A-12 &gt;

Polymer A-12 was obtained by sulfomethylation of polysulfone in accordance with the method described in Japanese Patent Laid-Open No. 2004-131662.

(34)

<< Synthesis of Polymer A-13 >>

Polymer A-13 was obtained in accordance with the method described in JP-A-2008-27890.

(35)

&Lt; Synthesis of Polymer A-14 &gt;

In a three-necked flask, 6.89 g of 4,4'-diaminobiphenyl-2,2'-disulfonic acid, 120 ml of m-cresol and 4.86 g of triethylamine were added and the solution became homogeneous Stir until. To this solution, 6.20 g of 4,4'-oxydiphthalic acid and 6.84 g of benzoic acid were added and the mixture was reacted at 80 DEG C for 4 hours and then at 180 DEG C for 20 hours. After the reaction temperature was returned to room temperature, the reaction solution was added dropwise to acetone. The resulting precipitate was filtered and dissolved in methanol, and the salt was then subjected to salt exchange with a proton type by Amberlyst 15 (hydrogen form) (manufactured by aldrich) to obtain 9.2 g of polymer A-14.

(36)

<< Synthesis of Polymer A-15 >>

J. Membr. Sci. Polymer A-15 was obtained by carrying out phosphomethylation of polysulfone in accordance with the method described in Journal of Organometallic Chemistry, vol.

(37)

<Synthesis of Copper Complex>

<< Synthesis of Copper Complex Cu-1 >>

556 mg of copper hydroxide was added to 20 g of a 20% aqueous solution of the polymer A-1, and the mixture was stirred at room temperature for 3 hours to dissolve the copper hydroxide. Thus, an aqueous solution of copper complex (hereinafter also referred to as engineering plastic copper complex) Cu-1 was obtained.

<< Synthesis of Copper Complex Cu-2 to Cu-17 >>

Copper complexes Cu-2 to Cu-17 were synthesized in the same manner as in the synthesis of the copper complex Cu-1, except that the mass ratio of the equivalent amount of the acid group of the polymer A1 to the equivalent amount of the copper atoms was changed as shown in Table 1 below.

[Table 1]

<< Synthesis of Copper Complex Cu-18 >>

3.00 g of ethanesulfonic acid and 3.76 g of butanesulfonic acid were diluted with 100 ml of methanol, 2.66 g of copper hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated, and the resulting solid was dried under reduced pressure to obtain a copper complex Cu-18.

<< Synthesis of copper complex Cu-19 >>

6.00 g of ethanesulfonic acid was diluted with 100 ml of methanol, 2.66 g of copper hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated, and the obtained solid was vacuum dried to obtain a copper complex Cu-19.

<< Synthesis of Copper Complex Cu-20 >>

To 20 g of a 20% aqueous solution of the polymer A-3, 1.84 g of copper acetate was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated with an evaporator, and the resulting acetic acid was removed. Water was added to the residue to obtain a 20% aqueous solution, whereby an aqueous solution of copper complex Cu-20 was obtained.

<< Synthesis of Copper Complex Cu-21 (Comparative Synthesis Example 1) >>

A copper complex Cu-21 was synthesized in the same manner as in the method described in Example 1 of JP-A-2011-227528.

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&Lt; Preparation of near infrared absorbing composition >

&Lt; Example 1 &gt;

&Lt; Adjustment of near infrared absorbing composition 1 >

The near infrared absorptive compositions of Examples 1 to 21 and Comparative Example 1 were prepared by mixing the copper complex and the solvent so that the blend amounts shown in Table 2 were obtained.

(II) hydrate (Wako Pure Chemical Industries, Ltd.) was used as the copper complex Cu-22 in Table 2, and the solvent EG was dissolved in ethylene glycol (Wako Pure Chemical Industries Co., Ltd. Manufactured by Wako Pure Chemical Industries, Ltd.) was used, and methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent MeOH.

[Table 2]

<Fabrication of near-infrared ray cut filter>

Each of the near infrared absorbing compositions prepared in Examples and Comparative Examples was applied to a glass substrate using an applicator application method (Baker applicator, YBA-3 type, manufactured by YOSHIMITS SEIKI, adjusted to a slit width of 250 mu m) (Prebaked) at 100 DEG C for 120 seconds. Thereafter, all the samples were heated at 180 DEG C for 180 seconds on a hot plate to obtain a near infrared ray blocking filter.

<Evaluation>

<< Evaluation of near infrared ray shielding >>

The transmittance at a wavelength of 800 nm in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The near infrared ray shielding property was evaluated by the following criteria.

A: transmittance at a wavelength of 800 nm &lt; = 5%

B: 5% <transmittance of 800 nm wavelength ≤7%

C: 7% <transmittance of 800 nm wavelength ≤10%

D: 10% <transmittance of 800 nm wavelength

<< Evaluation of moisture resistance >>

The near-infrared cut filter obtained as described above was allowed to stand under high temperature and high humidity of 85 占 폚 / 95% RH for 3 hours. (Abs λmax) at a wavelength of 700 to 1400 nm and a minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near infrared ray blocking filter were measured with a spectrophotometer U-4100 Manufactured by Hitachi High-Technologies Corporation), and the absorbance ratio represented by "Absλmax / Absλmin" was obtained. | Absorbance ratio before test (Absorbance ratio before test - Absorbance ratio after test) / Absorbance ratio before test 占 100 (%) The rate of change in absorbance was expressed by the following criteria.

A: Absorption ratio change rate ≤ 2%

B: 2% <change in absorbance ratio? 4%

C: 4% <change in absorbance ratio ≤7%

D: 7% <change in absorbance ratio

<< Heat resistance evaluation 1 >>

The near-infrared cut filter thus obtained was allowed to stand at 200 占 폚 for 5 minutes. (Abs λmax) at a wavelength of 700 to 1400 nm and a minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near infrared ray blocking filter were measured with a spectrophotometer U-4100 (Hitachi High- Manufactured by Technologies Inc.), and the absorbance ratio represented by "Absλmax / Absλmin" was obtained.

(Absorbance ratio before test / Absorbance ratio before test / Absorbance ratio before test) x 100 (%) was evaluated by the following criteria. The results are shown in Table 3 below.

A: Absorption ratio change rate ≤ 2%

B: 2% <change in absorbance ratio? 4%

C: 4% <change in absorbance ratio ≤7%

D: 7% <change in absorbance ratio

<< Heat resistance evaluation 2 >>

Evaluation was carried out in the same manner as in the heat resistance evaluation 1 except that the heating temperature was changed from 200 캜 to 265 캜.

[Table 3]

As is evident from Table 3, the near infrared absorbing composition of the Example was able to form a cured film having excellent heat resistance while maintaining a high near infrared ray shielding property as a cured film. In addition, the near infrared absorbing composition of the Examples was able to form a cured film having excellent moisture resistance.

On the other hand, the near infrared absorbing composition of the comparative example had poor heat resistance as a cured film as compared with the examples. In addition, the near infrared absorbing composition of the comparative example did not have good moisture resistance when it was used as a cured film, as compared with the examples.

&Lt; Example 23 &gt;

<< Preparation of near infrared absorptive composition >>

The following components were mixed in the amounts shown in Table 4 below to prepare the near infrared absorbing composition of Example 23. [

Copper complex A (copper complex having the following sulfophthalic acid as a ligand)

The engineering plastic copper complex Cu-1

The following binder A

The following surfactants A

· Solvent (water)

[Chemical Formula 39]

Binder A: The following compound (Mw: 24,000)

(40)

Surfactant A: Olin E1010 (manufactured by Nisshin Kagaku Kogyo K.K.)

(41)

Copper complex A was synthesized as follows.

A solution of 53.1% sulfophthalic acid in water (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and the solution was heated to 50 DEG C, copper hydroxide (2.84 g, 29.1 mmol) was added and the mixture was reacted at 50 DEG C for 2 hours. After completion of the reaction, the solvent and water generated were distilled off from the evaporator to obtain a copper complex A (8.57 g).

<< Examples 24 to 37 >>

The near infrared absorbing composition of Example 23 was obtained in the same manner as in Example 23 except that the engineering plastic copper complexes Cu-2 to Cu-15 were used instead of the engineering plastic copper complex Cu-1, respectively. A near infrared absorbing composition was prepared.

It was confirmed that the near infrared absorbing compositions of Examples 23 to 37 had higher near infrared absorbing ability.

[Table 4]

(A2) containing a monovalent ion and a compound containing a copper ion
2 Copper
3 main chain
4 side chains
Pentasaccharide ion site
10 silicon substrate
12 image pickup element
13 interlayer insulating film
14 base layer
15 Color filters
16 Overcoat
17 microlens
18 Light-shielding film
20 Adhesive
22 insulating film
23 metal electrode
24 solder resist layer
26 internal electrode
27 Element surface electrode
30 glass substrate
40 imaging lens
42 NIR filter
44 Shielded electronic shield
45 Adhesive
46 planarization layer
50 Lens Holder
60 solder balls
70 circuit board
100 solid-state imaging element substrate

Claims (17)

A compound obtained by a reaction of a polymer (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and an acid group or a salt thereof with a copper component. The method according to claim 1,
A near infrared absorbing composition, wherein the polymer (A1) comprises a constitutional unit represented by the following formula (A1-1);
[Chemical Formula 1]

In the formula (A1-1), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y ¹ represents a single bond or a divalent linking group, and X ¹ represents an acid group or a salt thereof. The method according to claim 1 or 2,
Wherein the polymer (A1) comprises a constituent unit represented by the following formula (A1-2);
(2)

Formula (A1-2) of, Ar ² represents an aromatic hydrocarbon group and / or aromatic heterocyclic group, Y ² denotes a single bond or a divalent connecting group, X ² represents an acid group or a salt thereof, Y ³ represents a single _{bond, -O-, -S-, -SO 2 -} , -CO-, -C (= O) O-, -OC (= O) O-, -P (= O) R 0 -, -CR 1 R ² - or -C (= O) NR ³ -; R ⁰ represents a hydrogen atom, a hydrocarbon group, or a hydroxyl group; R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group; R ³ represents a hydrogen atom or a hydrocarbon group. The method of claim 2,
The divalent linking group may be a linear, branched or cyclic alkylene group, an arylene group, -O-, -S-, -C (= O) -, -C (= O) O-, Wherein the near infrared absorptive composition shows a group formed. The method according to any one of claims 1 to 4,
Wherein the acid group or a salt thereof is selected from at least one member selected from a carboxylic acid group and a salt thereof, a phosphoric acid group and a salt thereof, a phosphonic acid and a salt thereof, and a sulfonic acid group and a salt thereof. The method according to any one of claims 1 to 5,
Wherein the acid group or a salt thereof is selected from at least one selected from a carboxylic acid group and a salt thereof and a sulfonic acid group and a salt thereof. 7. The method according to any one of claims 1 to 6,
Wherein the polymer (A1) has a weight average molecular weight of 1,000 to 10,000,000. The method according to any one of claims 1 to 7,
Further comprising water. (A2) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and an acid group ion as a ligand. (A1) having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in its main chain and having an acid group or a salt thereof, and a compound obtained by the reaction of a copper component,
A low molecular weight compound containing an acid group or a salt thereof and a copper complex obtained by a reaction of a copper component
Absorbent composition. The method of claim 10,
Wherein the molecular weight of the low-molecular compound is 1000 or less. The method according to claim 10 or 11,
Wherein the low-molecular compound includes at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom. A near infrared ray blocking filter obtained by using the near infrared absorbing composition according to any one of claims 1 to 12. 14. The method of claim 13,
A near infrared ray blocking filter having a rate of change of an absorbance ratio determined by the following equation before and after heating at 200 DEG C for 5 minutes is 5% or less;
[(Absorbance ratio before heating - Absorbance ratio after heating) / Absorbance ratio before heating]
Here, the term "absorbance ratio" refers to a value obtained by dividing the maximum absorbance at a wavelength of 700 to 1400 nm by the minimum absorbance at a wavelength of 400 to 700 nm. A method for manufacturing a near-infrared light blocking filter, comprising the step of forming a film on the light receiving side of a solid-state imaging element substrate by applying the near infrared absorbing composition according to any one of claims 1 to 12. Wherein the solid-state imaging element substrate and the near infrared ray blocking filter disposed on the light receiving side of the solid-state imaging element substrate, wherein the near infrared ray blocking filter is the near infrared ray blocking filter according to claim 13 or claim 14. 1. A manufacturing method of a camera module having a solid-state imaging element substrate and a near-infrared cut-off filter disposed on a light-receiving side of the solid-state imaging element substrate, characterized in that, on the light receiving side of the solid- And a step of forming a film by applying the near infrared absorbing composition.

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