TW201502147A - Near-infrared absorbing composition, near-infrared cut filter using the same, manufacturing method thereof, camera module and manufacturing method thereof - Google Patents

Abstract

A near infrared absorptive composition, a near infrared cut filter using the same and a method for manufacturing the same and a camera module and a method for manufacturing the same are provided, wherein the near infrared absorptive composition forms a cured film which maintains a high near infrared shielding property and is excellent in heat resistance. The near infrared absorptive composition of the invention contains a compound obtained from a reaction of a polymer (A1) and a copper component, wherein the polymer (A1) has an aromatic hydrocarbon group and/or an aromatic heterocyclic group in a main chain, and contains an acid group or a salt thereof.

Description

Near-infrared absorbing composition, near-infrared cut filter using the same, manufacturing method thereof, camera module and manufacturing method thereof

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

In a video camera, a digital still camera, a mobile phone with a camera function, etc., a charge-coupled device (CCD) or a complementary image of a solid-state imaging device as a color image is used. Metal oxide semiconductor (Complementary Metal-Oxide-Semiconductor, CMOS) image sensor. The solid-state imaging device uses a silicon photodiode that is sensitive to near-infrared light in the light-receiving portion. Therefore, it is necessary to perform visual sensitivity correction. In many cases, a near-infrared cut filter (hereinafter also referred to as an IR cut filter) is used. .

As a material of the near-infrared cut filter, there is disclosed in Patent Document 1 An infrared-blocking film containing an infrared blocking resin which is a reactant of (meth)acrylamide and phosphoric acid or a hydrolyzate thereof, and a compound having an ethylenically unsaturated bond In the copolymer, a metal compound is added.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-134457

Here, the infrared blocking resin disclosed in Patent Document 1 has been studied, and as a result, it has been found that heat resistance is insufficient.

An object of the present invention is to provide a near-infrared absorbing composition capable of forming a cured film having high near-infrared ray shielding properties and excellent heat resistance.

As a result of intensive studies, the present inventors have found that the problem can be solved by using a compound obtained by a reaction of a polymer (A1) having an aromatic hydrocarbon group in a main chain. And at least one of the aromatic heterocyclic groups, and contains an acid group or a salt thereof. Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <17>.

<1> A near-infrared absorbing composition comprising a compound obtained by reacting a polymer (A1) with a copper component, wherein the polymer (A1) has an aromatic hydrocarbon group and/or an aromatic hybrid in a main chain a ring group and containing an acid group or a salt thereof.

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

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) contains a structural unit represented by the following formula (A1-2);

In the formula (A1-2), Ar ² represents an aromatic hydrocarbon group and/or an aromatic heterocyclic group, Y ² represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof, and 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; and R ³ represents a hydrogen atom or a hydrocarbon group.

<4> a near-infrared absorbing composition as described in <2> or <3>, The divalent linking group represents a linear, branched or cyclic alkyl, aryl, -O-, -S-, -C(=O)-, -C(=O)O- or The combined groups of these.

The near-infrared absorbing composition according to any one of <1> to <4> wherein the acid group or a salt thereof is selected from the group consisting of a carboxylic acid group and a salt thereof, a phosphate group and a salt thereof, and a phosphonic acid group. And a salt thereof, and at least one of a sulfonic acid group and a salt thereof.

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

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 10,000,000.

<8> The near-infrared absorbing composition according to any one of <1> to <7> which further contains water.

<9> A near-infrared absorbing composition containing a copper complex which is a polymer having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain and containing an acid group ion ( The acid-based ion moiety of A2) acts as a ligand.

<10> A near-infrared absorbing composition comprising a reaction of a polymer (A1) having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in an main chain and containing an acid group or a salt thereof, and a copper component; a compound; and a copper complex obtained by a reaction of a low molecular compound containing an acid group or a salt thereof and a copper component.

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

<12> The near-infrared absorbing composition according to <10>, wherein the low molecular compound contains 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-eliminating filter obtained by using the near-infrared absorbing composition according to any one of <1> to <12>.

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

[(Absorbance ratio before heating - Ratio of absorbance after heating) / Absorbance ratio before heating]

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

<15> A method of producing a near-infrared-ray cut filter, comprising the step of: applying a near-infrared absorbing composition according to any one of <1> to <12> to a light receiving side of a solid-state image sensor substrate, Thereby a film is formed.

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

<17> A method of manufacturing a camera module, which has a solid-state imaging element a substrate and a camera module disposed on a light-receiving side near-infrared cut filter of the solid-state imaging device substrate, and the method of manufacturing the camera module includes the step of coating the light-receiving side of the solid-state imaging device substrate such as <1 The near-infrared absorbing composition according to any one of <12>, wherein a film is formed.

According to the present invention, it is possible to provide a cured film which maintains high near-infrared shielding properties and is excellent in heat resistance.

1‧‧‧Compounds containing acid-based ions (A2) and copper ions

2‧‧‧Copper ion

3‧‧‧Main chain

4‧‧‧ side chain

5‧‧‧ Acid-based ion sites

10‧‧‧矽 substrate

12‧‧‧Photographic components

13‧‧‧Interlayer insulating film

14‧‧‧Material layer

15‧‧‧Color filters

15B‧‧‧Blue color filter

15G‧‧‧Green color filter

15R‧‧‧Red color filter

16‧‧‧Overcoat

17‧‧‧Microlens

18‧‧‧Shade film

20, 45‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧solder layer

26‧‧‧Internal electrodes

27‧‧‧ Component surface electrode

30‧‧‧ glass substrate

40‧‧‧ camera lens

42‧‧‧Near-infrared cut-off filter

44‧‧‧Shading and electromagnetic shielding

46‧‧‧Destivation layer

50‧‧‧Lens mount

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

200‧‧‧ camera module

Hν‧‧‧ incident light

Fig. 1 is a view showing an example of a compound containing a polymer (A2) and a copper ion of the present invention.

FIG. 2 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state imaging element according to an embodiment of the present invention.

3 is a schematic cross-sectional view showing 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 in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means acrylonitrile group and Methyl methacrylate.

In this specification, "single" has the same meaning as "monomer" and, in addition, "poly "Compound" has the same meaning as "polymer".

In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having a substituent.

The term "near infrared ray" as used in the present invention means that the maximum absorption wavelength ranges from 700 nm to 2500 nm, particularly from 700 nm to 1000 nm.

The term "near-infrared absorbing property" as used in the present invention means having a maximum absorption wavelength in the near-infrared range.

The main chain of the polymer in the present invention refers to an atom or a group of atoms necessary for forming a skeleton (long chain) of the polymer, and when a part or all of the skeleton is a cyclic group (for example, an aryl group), This cyclic group is also considered to be part of the main chain. In addition, atoms that are directly bonded to the main chain are also considered to be part of the main chain. The side chain of the polymer in the present invention means a portion other than the main chain. Among them, a functional group directly bonded to the main chain (for example, an acid group or a salt thereof described later) is also regarded as a side chain.

<Near Infrared Absorbing Composition of the Present Invention>

The first near-infrared absorbing composition of the present invention is characterized by comprising a compound obtained by a reaction of a polymer (A1) with a copper component, wherein the polymer (A1) has an aromatic hydrocarbon group in the main chain and/or An aromatic heterocyclic group and an acid group or a salt thereof.

Further, the second near-infrared absorbing composition of the present invention contains a polymer (A1) and a copper having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain and containing an acid group or a salt thereof. a compound obtained by the reaction of the component; and a copper complex obtained by a reaction of a low molecular compound containing an acid group or a salt thereof and a copper component.

Since the near-infrared absorbing composition of the present invention contains a compound obtained by the reaction of the polymer (A1) and the copper component, it is possible to form a cured film which maintains high near-infrared ray shielding properties and is excellent in heat resistance when it is formed into a cured film. Although the reason is speculation, it can be considered as follows.

The compound obtained by the reaction of the polymer (A1) with the copper component is, for example, a compound containing an acid group-containing polymer (A2) and a copper ion, preferably in the form of an acid-based ion in the polymer (A2). Copper complex as a ligand. Fig. 1 is a view showing an example of a compound containing a polymer-containing ion-containing polymer (A2) and a copper ion, and 1 represents a compound containing an acid group-containing polymer (A2) and a copper ion, and 2 represents a copper ion. 3 denotes a main chain of the polymer (A2), 4 denotes a side chain of the polymer (A2), and 5 denotes an acid-based ion site derived from an acid group or a salt thereof. In the present invention, the acid-based ion site 5 is bonded to the copper ion 2 (for example, to form a coordinate bond), and a copper is used as a starting point to form a crosslinked structure between the side chains 4 of the polymer (A2). By setting such a configuration, it is presumed that the structure of the compound 1 is not easily broken even by heating, and as a result, a cured film excellent in heat resistance can be obtained. Further, since the polymer (A2) has at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain 3, a cured film having more excellent heat resistance can be obtained.

Further, in the present invention, by using a compound obtained by a reaction of the polymer (A1) with a copper component, the content of copper in the composition can be further increased, and there is an advantage that copper is not easily peeled off even when heated.

Further, 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% by mass to 25% by mass, more preferably It is 7 mass% to 20 mass%, and more preferably 8 mass% to 15 mass%.

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

Further, in the second near-infrared absorbing composition of the present invention, the content of the compound obtained by the reaction of the polymer (A1) and the copper component with respect to the total solid content in the composition is preferably 10% by mass to 90% by mass. % is more preferably 15% by mass to 80% by mass, further preferably 15% by mass to 70% by mass, and still more preferably 20% by mass to 70% by mass.

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

<<Bronze ingredients>>

The copper component is more preferably a compound containing divalent copper. The copper content in the copper component used in the present invention is preferably from 2% by mass to 90% by mass, more preferably from 10% by mass to 70% by mass. The copper component may be used alone or in combination of two or more.

As the copper component used in the present invention, for example, copper or a compound containing copper can be used. As the copper-containing compound, for example, copper oxide or a copper salt can be used. The copper salt is preferably monovalent copper or divalent copper, more preferably divalent copper. Examples of the copper salt include copper hydroxide, copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetate, copper pyrophosphate, copper naphthenate, copper citrate, and nitric acid. Copper, copper sulfate, copper carbonate, copper chlorate, copper (meth)acrylate, copper perchlorate, further preferably copper hydroxide, copper acetate, chlorination Copper, copper sulfate, copper benzoate, copper (meth)acrylate, particularly preferably copper hydroxide, copper acetate and copper sulfate.

The amount of the copper component to be reacted with the polymer (A1) is preferably from 0.01 equivalents to 1 equivalent, more preferably from 0.1 equivalents to 0.6 equivalents, even more preferably 0.4, based on 1 equivalent of the acid group of the polymer (A1) or a salt thereof. Equivalent to 0.5 equivalents. By setting the amount of copper in the copper component to such a range, there is a tendency to obtain a cured film having a higher near-infrared shielding property.

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

The polymer (A1) has an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain. The polymer (A1) may have at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain, and may have two or more types. The polymer (A1) may be used alone or in combination of two or more.

The aromatic hydrocarbon group is, for example, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms, particularly preferably a phenyl group, a naphthyl group or a phenyl group. Phenyl. The aromatic hydrocarbon group may be monocyclic or polycyclic, preferably monocyclic.

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. Further, the aromatic heterocyclic group is a monocyclic ring or a condensed ring, and examples thereof include a monocyclic ring or a condensed ring having a condensation number of 2 to 8. The hetero atom contained in the hetero ring may be a nitrogen, an oxygen or a sulfur atom, preferably nitrogen or oxygen.

In the case where the aromatic hydrocarbon group and/or the aromatic heterocyclic group has the substituent T, the substituent T may, for example, be an alkyl group or a polymerizable group (preferably a polymer having a carbon-carbon double bond) A compatible group), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxylate group, a halogenated alkyl group, an alkoxy group, a methacryloxy group, an acryloxy group, an ether group, a sulfonate A mercapto group, a thioether group, a decylamino group, a decyl group, a hydroxyl group, a carboxyl group, an aralkyl group or the like is preferably an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms).

In particular, the polymer (A1) is preferably selected from the group consisting of polyether fluorene-based polymers, polyfluorene-based polymers, polyether ketone polymers, polyphenylene ether polymers, polyimine polymers, polybenzimidazoles. At least one of a polymer, a polyphenyl polymer, a phenol resin polymer, a polycarbonate polymer, a polyamide polymer, and a polyester polymer. Examples of the respective polymers are shown below.

Polyether fluorene-based polymer: a polymer having a main chain structure represented by (-O-Ph-SO ₂ -Ph-) (Ph represents a phenyl group, the same applies hereinafter)

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

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

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

Polyphenylene polymer: a polymer having a main chain structure represented by (-Ph-)

Phenolic resin-based polymer: a polymer having a main chain structure represented by (-Ph(OH)-CH ₂ -)

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

The polyamine polymer is, for example, a polymer having a main chain structure represented by (-Ph-C(=O)-NH-)

The polyester-based polymer is, for example, a polymer having a main chain structure represented by (-Ph-C(=O)O-)

The polyether fluorene-based polymer, the polyfluorene-based polymer, and the polyether ketone-based polymer can be referred to, for example, in paragraph 0022 of JP-A-2006-310068 and paragraph 0028 of JP-A-2008-27890. The main chain structure, which is incorporated into the specification of the present application.

The polyimine-based polymer can be referred to the main chain structure described in paragraphs 0047 to 0059 of JP-A-2002-367627, and 0018 to 0019 of JP-A-2004-35891. The content is incorporated into the specification of the present application.

The polymer (A1) contains an acid group or a salt thereof, and the acid group or a salt thereof may be used alone or in combination of two or more.

The acid group of the polymer (A1) is not particularly limited as long as it can react with the copper component, and it is preferred to form a coordinate bond with the copper component. For example, an acid group having an acid dissociation constant (pKa) of 5 or less is preferable, and a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a quinone group or the like is preferable.

The atom or the atomic group constituting the salt of the acid group used in the present invention may be an atomic group such as a metal atom such as sodium (particularly an alkali metal atom) or tetrabutylammonium, preferably a metal atom, more preferably an alkali metal. atom.

Further, in the polymer (A1), the acid group or a salt thereof is contained in the main chain and the side thereof. Preferably, at least one of the chains may be contained in at least one of the side chains. In particular, in the polymer (A1), the acid group or a salt thereof is preferably bonded to the aromatic hydrocarbon group and/or the aromatic heterocyclic group directly or via a linking group.

The acid group or a salt thereof preferably contains, for example, at least one selected from the group consisting of a carboxylic acid group and a salt thereof, a phosphate group and a salt thereof, a phosphonic acid group and a salt thereof, and a sulfonic acid group and a salt thereof.

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

Further, 99 mol% (% by mole) or more of all the acid groups in the polymer (A1) are preferably selected from the group consisting of a carboxylic acid group and a salt thereof, a phosphate group and a salt thereof, a phosphonic acid group and a salt thereof, and a sulfonic acid. At least one of a base and a salt thereof. It is particularly preferable that 99 mol% or more of all the acid groups in the polymer (A1) are at least one selected from the group consisting of 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), and more preferably a structural unit represented by the following formula (A1-2).

(In the formula (A1-1) and the formula (A1-2), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y ¹ and Y ² each independently represent a single bond or two The valency linking group, X ¹ and X ² each independently represent an acid group or a salt thereof. In the formula (A1-2), Y ³ represents a single bond, -O-, -S-, -SO ₂ -, -CO-, -C(=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 -(R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group) or -C(=O)NR ³ - (R ³ represents a hydrogen atom or a hydrocarbon group))

In the case of the formula (A1-1) and the formula (A1-2), when Ar ¹ represents an aromatic hydrocarbon group, the same meaning as the aromatic hydrocarbon group is used, and the preferred range is also the same. When Ar ¹ represents an aromatic heterocyclic group, it has the same meaning as the above aromatic heterocyclic group, and the preferred range is also the same.

In addition to Ar ¹ in the formula (A1-1) -Y ¹ -X ¹ may have a substituent, further, in addition to Ar ² in the formula (A1-2) -Y ² -X ² than may have a substituent. In the case where Ar ¹ and Ar ² have a substituent, the substituent has the same meaning as the substituent T, and the preferred range is also the same.

In the formula (A1-1), Y ¹ and Y ^{2 are} preferably a single bond. In the case where 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)O-, -OC(=O)-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), -C(R ^Y1 )(R ^Y2 )- Or a group comprising such combinations. 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 a linear, branched or cyclic alkylene group or an extended aryl group. The linear alkyl group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. The branched alkyl group is preferably an alkylene group having 3 to 20 carbon atoms, more preferably an alkylene group having 3 to 10 carbon atoms, and more preferably an alkylene group having 3 to 6 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. 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 more preferably a cycloalkyl group having 6 to 10 carbon atoms. For the linear, branched or cyclic alkylene groups, the hydrogen atom in the alkyl group may also be substituted by a fluorine atom.

The aryl group is preferably an extended aryl group having 6 to 18 carbon atoms, more preferably an extended aryl group having 6 to 14 carbon atoms, and more preferably an extended aryl group having a carbon number of 6 to 10, and particularly preferably a phenyl group.

The aromatic heterocyclic group is not particularly limited, and is preferably a 5-membered ring or a 6-membered ring. Further, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4.

In particular, when Y ¹ and Y ² in the formula (A1-1) and the formula (A1-2) represent a divalent linking group, it is preferably a linear or branched or cyclic alkyl group or an aromatic group. a group, -O-, -S-, -CO-, -C(=O)O-, or a group comprising such a combination. More preferably, it is -S-, -C(R ^X1 )(R ^X2 )-(R ^X1 and R ^X2 preferably each independently represent an alkyl group or a fluorine atom having 1 to 3 carbon atoms), and a carbon number of 1 to 3 An alkyl group, or a group comprising such combinations.

In the formula (A1-1) and the formula (A1-2), the acid group represented by X ¹ and X ² or a salt thereof has the same meaning as the acid group or a salt thereof, and the preferred range is also the same.

In the case of 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 and a carbon number of 6 to 12 Aryl.

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

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

The weight average molecular weight of the polymer (A1) is preferably 1,000 or more, more preferably from 1,000 to 10,000,000, and further preferably from 3,000 to 1,000,000, particularly preferably from 4,000 to 400,000. When the weight average molecular weight of the polymer (A1) is set to such a range, the moisture resistance of the obtained cured film tends to be further improved.

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

[Chemical 4]

[Chemical 5]

[化10]

The near-infrared absorbing composition of the present invention may contain a compound obtained by reacting the polymer (A1) with a copper component, and may be blended with other near-infrared absorbing compounds, solvents, curable compounds, and binder polymers, if necessary. Surfactant, polymerization initiator, and other ingredients.

Further, in the near-infrared absorbing composition of the present invention, a compound containing an acid group or a salt thereof for obtaining another near-infrared absorbing compound described later may be blended.

<Other near infrared absorbing compounds>

In the composition of the present invention, in order to further improve the near-infrared absorbing ability, the compound obtained by the reaction of the polymer (A1) and the copper component may be blended. Near infrared absorbing compound. 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 a normal maximum absorption wavelength range of 700 nm to 2500 nm, preferably 700 nm to 1000 nm (near infrared ray range).

The other near-infrared absorbing compound is preferably a copper compound, more preferably a copper complex. Further, in the case of blending other near-infrared absorbing compounds, the ratio (mass ratio) of the compound obtained by the reaction of the polymer (A1) with the copper component to other near-infrared absorbing compounds is preferably 10:90 to 95: 5, more preferably 20:80~90:10, and then 20:80~80:20.

The molecular weight of the other near-infrared absorbing compound is not particularly limited, but is preferably from 70 to 1,000, more preferably from 130 to 500.

When the other near-infrared absorbing compound is a copper complex, the ligand L to be placed on the copper is not particularly limited as long as it can form a coordinate bond with the copper ion, and examples thereof include a sulfonic acid and a carboxylic acid. Acid, phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid, substituted phosphinic acid, carbonyl (ester, ketone), amine, decylamine, sulfonamide, urethane, urea, alcohol, sulfur A compound such as an alcohol. Among these compounds, a carboxylic acid and a sulfonic acid are preferred, and a sulfonic acid is more preferred.

Specific examples of the copper complex compound include a phosphorus-containing copper compound, a copper sulfonate compound, or a copper compound represented by the following formula (A). Specifically, for example, the compound described in WO2005/030898, page 5, line 27 to page 7, line 20, may be incorporated into the specification of the present application.

The copper complex compound is, for example, a copper complex represented by the following formula (A).

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

In the formula (A), L represents a ligand coordinated to copper, X is absent, or represents a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, BF ₄ , PF ₆ , BPh ₄ (Ph represents phenyl) or alcohol. N1 and n2 each independently represent an integer of 1 to 4.

The ligand L has a substituent containing C, N, O, and S as an atom which can be coordinated to copper, and more preferably a group having an isolated electron pair containing N or O, S or the like. The group which can be coordinated is not limited to one type in the molecule, and may contain two or more types, and may be dissociated or non-dissociated. In the case of non-dissociation, X does not exist.

The copper complex is a copper compound in which a ligand is coordinated to copper of a central metal, and copper is usually divalent copper. For example, it can be obtained by mixing a copper component into a ligand compound or a salt thereof, and performing a reaction or the like.

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

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

General formula (i)

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

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

In the case where the hydrocarbon group is monovalent, it is preferably an alkyl group or an aryl group, more preferably an aryl group. In the case where the hydrocarbon group is divalent, it is preferably an alkyl group, an aryl group, an alkyl group, and more preferably an aryl group. Further, when the hydrocarbon group is trivalent or higher, a group corresponding to the hydrocarbon group is preferred.

The alkyl group or alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

The carbon number of the aryl or aryl group is preferably from 6 to 18, more preferably from 6 to 12.

In the 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 one type or two or more types, and preferably two or more types.

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

The molecular weight of the compound to be ligand or a salt thereof (compound containing an acid group or a salt thereof) is preferably 1,000 or less, preferably 70 to 1,000, and 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, and more preferably (2) having two The above aspect of the acid group is further preferably (3) having a sulfonic acid group and a carboxylic acid group. These aspects can more effectively exert infrared absorption capability. Enter 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 compounds. Further, specific examples of the compound having a sulfonic acid group include specific examples of the sulfonic acid compound represented by the following formula (I). Further, a compound corresponding to the present aspect among the compounds described in the aspect (2) and the aspect (3) described later is preferable.

(2) Specific examples of the compound having at least two acid groups are as follows. Further, a compound corresponding to the present aspect among the compounds described in the aspect (3) described later is also preferably used.

[Chemistry 13]

(3) Specific examples of the compound having a sulfonic acid group and a carboxylic acid group include the following compounds. Further, specific examples of the compound having a sulfonic acid group and a carboxylic acid group represented by the following formula (I) can also be mentioned.

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

Formula (I)

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

The specific monovalent organic group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group, an alkenyl group, and an aryl group. Here, the groups may also be a divalent linking group (eg, alkyl, cycloalkyl, aryl, -O-, -S-, -CO-, -C(=O)O). a group of -, -OCO-, -SO ₂ -, -NR- (R is a hydrogen atom or an alkyl group). Further, the monovalent organic group may have a substituent.

The linear or branched alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.

The cyclic alkyl group may be either a single ring or a polycyclic ring. 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 further preferably a cycloalkyl group having 6 to 10 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms.

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 more preferably an aryl group having 6 to 10 carbon atoms.

Examples of the alkylene group, the cycloalkylene group and the extended aryl group as the divalent linking group include a divalent linking group obtained by deriving one hydrogen atom from the alkyl group, the cycloalkyl group or the aryl group described above.

The substituent which the monovalent organic group may have is exemplified by an alkyl group, a polymerizable group (e.g., a vinyl group, a (meth) propylene group, an epoxy group, an oxetanyl group, etc.), a halogen atom, a carboxyl group, or a carboxyl group. An acid ester group (for example, -CO ₂ CH ₃ or the like), a hydroxyl group, a decylamino group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group) or the like.

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

Specific examples of the compound represented by the formula (I) are shown below, but are not limited to these specific examples.

[化17]

The sulfonic acid compound which can be used in the present invention can be synthesized by using a commercially available sulfonic acid or by a known method. The salt of the sulfonic acid compound which can be used in the present invention is, for example, a metal salt, and specific examples thereof include a sodium salt and a potassium salt.

In addition to the copper complex, other copper complexes which can be used in the present invention include copper complexes in which a carboxylic acid is used as a ligand. As the carboxylic acid used in the copper complex which has a carboxylic acid as a ligand, for example, a compound represented by the following formula (K) can be used.

(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, and for example, has the same meaning as the monovalent organic group in the formula (I).

(inorganic particles)

The composition of the present invention may contain inorganic fine particles as other near-infrared absorbing compounds. The inorganic fine particles may be used singly or in combination of two or more.

The inorganic fine particles are particles which mainly function to block (absorb) infrared rays. In terms of being more excellent in infrared light blocking property, the inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles.

Examples of the inorganic fine particles include Indium Tin Oxide (ITO) particles, Antimony Tin Oxide (ATO) particles, aluminum-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped dioxide. Metal oxide particles such as tin (F-doped SnO ₂ ) particles or erbium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, or silver (Ag) particles, gold (Au) particles, copper (Cu) particles or nickel (Ni) ) Metal particles such as particles. Further, in order to have both infrared ray blocking property and photo lithography, it is preferable that the transmittance at the exposure wavelength (365 nm to 405 nm) is high, and indium tin oxide (ITO) particles or strontium tin oxide (ATO) particles are preferable.

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

In addition, a tungsten oxide-based compound can be used as the inorganic fine particles, and specifically, a tungsten oxide-based compound represented by the following general formula (composition formula) (I) is more preferable.

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

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

0.001≦x/y≦1.1

2.2≦z/y≦3.0

Examples of the metal of M include alkali metal, alkaline earth metal, magnesium (Mg), zirconium (Zr), chromium (Cr), manganese (Mn), iron (Fe), ruthenium (Ru), cobalt (Co), and rhodium (Rh). ), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), aluminum (Al ), gallium (Ga), indium (In), tantalum (Tl), tin (Sn), lead (Pb), titanium (Ti), niobium (Nb), vanadium (V), molybdenum (Mo), tantalum (Ta) And 铼 (Re), 铍 (Be), 铪 (Hf), 锇 (Os), 铋 (Bi), preferably an alkali metal, preferably Rb or Cs, more preferably Cs. The metal of M may be one type or two or more types.

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when x/y is 1.1 or less, it is possible to more reliably prevent the formation of an impurity phase in the tungsten oxide-based compound.

By having z/y of 2.2 or more, the chemical stability of the material can be further improved, and by z/y being 3.0 or less, infrared rays can be sufficiently shielded.

The metal oxide is preferably tantalum tungsten oxide.

Specific examples of the tungsten oxide based compound of general formula (I) represented _{include: Cs 0.33 WO 3, Rb 0.33} WO 3, K 0.33 WO 3, Ba 0.33 WO 3 and the like, preferably Rb or Cs _0.33 WO _{3 0.33} WO ₃ , more preferably Cs _0.33 WO ₃ .

The metal oxide is preferably a microparticle. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. Since the average particle diameter is in such a range, the metal oxide is less likely to block visible light by light scattering, so that light transmittance in the visible light range can be made more reliable. From the viewpoint of avoiding light scattering, the average particle diameter is preferably as small as possible, but the average particle diameter of the metal oxide is usually 1 nm or more for reasons such as ease of handling during production.

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

The content of the metal oxide is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably from 1% by mass to 10% by mass based on the total solid content of the metal oxide-containing composition. quality%.

<solvent>

The solvent to be used in the present invention is not particularly limited, and may be appropriately selected according to the purpose, as long as the components of the composition of the present invention are uniformly dissolved or dispersed. For example, an aqueous solvent such as water or alcohol can be preferably used. Further, in addition to the above, the solvent used in the present invention may preferably be an organic solvent, a ketone, an ether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and dimethylformamide or dimethylamine. Indoleamine, dimethyl hydrazine, cyclobutyl hydrazine and the like. These solvents may be used alone or in combination of two or more.

Specific examples of the alcohol, the aromatic hydrocarbon, and the halogenated hydrocarbon are described in paragraph 0136 of JP-A-2012-194534, and the contents thereof are incorporated in the specification of the present application. Further, specific examples of the esters, ketones, and ethers include Japan. JP-A-2012-208494, paragraph 0497 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the specification of [0609]), further includes n-amyl acetate, ethyl propionate, and phthalic acid. Dimethyl formate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate, and the like.

It is especially preferred that the composition of the present invention contains water. The water is preferably contained in an amount of 40% by mass to 95% by mass based on the composition of the present invention, and more preferably 50% by mass to 85% by mass based on the composition of the present invention.

When the composition of the present invention contains a solvent other than water, it is preferred to contain a solvent other than water in a ratio of 40% by mass to 90% by mass based on the composition of the present invention. The solvent other than water may be used alone or in combination of two or more.

<hardening 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. Further, it may be a thermosetting compound or a photocurable compound, and the thermosetting composition is preferred because of its high reaction rate.

<<Compound with polymerizable group>>

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

<<Polymerizable monomer and polymerizable oligomer>>

The composition of the present invention may also contain a monomer having a polymerizable group (polymerizable monomer) Or an oligomer (polymerizable oligomer) having a polymerizable group (hereinafter, a polymerizable monomer and a polymerizable oligomer are collectively referred to as a "polymerizable monomer") as a polymerizable compound.

Examples of the polymerizable monomer and the like include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines, and preferably no. An ester of a saturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, the following reactants can also be preferably used: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group or an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. a reactant, or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, or the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether or allyl ether may be used instead of the unsaturated carboxylic acid.

For the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 is preferably used in the present invention.

In addition, the polymerizable monomer or the like may also be used to have at least one A compound having an ethylenically unsaturated group having an addition-polymerized vinyl group and having a boiling point of 100 ° C or higher at normal pressure may be a monofunctional (meth) acrylate or a difunctional group (A) A acrylate, a trifunctional or higher (meth) acrylate (for example, a trifunctional to hexafunctional (meth) acrylate).

Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(a) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene oxypropyl) ether , (tris-propenyloxyethyl) iso-cyanate, (meth)acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane a compound.

As the polymerizable compound, a vinyloxy-modified pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available as Kyala) can be used. (KAYARAD) D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol (Meth) acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercial product is Kayad ( KAYARAD) DPHA; manufactured by Nippon Kayaku Co., Ltd., and the structure of these (meth)acryloyl sulfhydryl groups separated by ethylene glycol and propylene glycol residues. In addition, such oligomer types can also be used. Japanese patents can also be opened The compound described in Paragraph No. 0248 to Paragraph No. 0251 of No. 2007-269779 is used in the present invention.

The polymerizable monomer and the like described in paragraph 0477 of the Japanese Patent Laid-Open Publication No. 2012-208494 (the corresponding Japanese Patent Application Publication No. 2012/0235099 [0585]), etc. Incorporated into the specification of the present application. Further, it is also possible to use Ethylene Oxide (EO) modified (meth) acrylate (commercially available as M-460; manufactured by Toagosei Co., Ltd.). Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) can also be used. These types of oligomers can also be used.

For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group may be used by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. Polyfunctional monomer. For example, M-305, M-510, M-520, etc. of the Aronix series which is a polyacid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. can be mentioned.

The polyfunctional monomer having an acid group has an acid value of from 0.1 mg-KOH/g to 40 mg-KOH/g, particularly preferably from 5 mg-KOH/g to 30 mg-KOH/g. In the case where a polyfunctional monomer having two or more acid groups is used in combination, or a combination of a polyfunctional monomer having no acid group, the acid value of the entire polyfunctional monomer must be within the above range. Adjustment.

<<Polymer with polymerizable group on side chain>>

The second aspect of the composition of the present invention may also be a form containing a polymer having a polymerizable group in a side chain as a polymerizable compound. The polymerizable group may, for example, be an ethylenically unsaturated double bond group, an epoxy group or an oxetanyl group.

<<Compounds having an epoxy group or an oxetane group>>

The third aspect of the present invention is a form containing a compound having an epoxy group or an oxetane group as a polymerizable compound. The compound having an epoxy group or an oxetanyl group specifically has a polymer having an epoxy group in a side chain and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule. Listed: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, and the like. Further, a monofunctional or polyfunctional glycidyl ether compound can also be mentioned.

These compounds can be used as a commercial product, and can also be obtained by introducing an epoxy group into a side chain of a polymer. For the commercial product, for example, the description of paragraph 0191 of Japanese Patent Laid-Open Publication No. 2012-155288, and the like is incorporated herein by reference.

Further, commercially available products include: Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, and Denacol EX- 321L, a polyfunctional aliphatic glycidyl ether compound such as Denacol EX-850L (above, manufactured by Nagase Chemtex). These compounds are low-chlorine products, and EX-212, EX-214, EX-216, EX-321, EX-850, etc. which are not low-chlorine products can also be used in the same manner.

In addition, there are also: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, Adico resin (ADEKA RESIN) EP-4010S, ADEKA RESIN EP-4011S (above ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is manufactured by ADEKA), JER1031S, etc.

Further, commercially available products of the phenol novolac type epoxy resin include JER-157S65, JER-152, JER-154, and JER-157S70 (the above are manufactured by Mitsubishi Chemical Corporation).

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule can be used. Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (the above is manufactured by East Asia Synthetic Co., Ltd.).

In the case where the group is introduced into the side chain of the polymer to carry out the synthesis, the introduction reaction can be carried out, for example, by subjecting a tertiary amine such as triethylamine or benzylmethylamine to chlorinated twelve. a quaternary ammonium salt such as alkyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride, pyridine or triphenylphosphine as a catalyst, in an organic solvent at a reaction temperature of 50 ° C to 150 ° C The reaction takes several hours to several tens of hours. The introduction amount of the alicyclic epoxy unsaturated compound can be such that the acid value of the obtained polymer satisfies 5 KOH. Mg/g~200KOH. The range of mg/g is controlled in a manner. Further, the molecular weight may be set to a range of 500 to 5,000,000, and further preferably 1000 to 500,000 by weight.

Epoxy unsaturated compounds may also use glycidyl (meth)acrylate or allylic A glycidyl group such as a glycidyl ether has a glycidyl group as an epoxy group. Such a compound can be referred to, for example, the description of paragraph 0045 of JP-A-2009-265518, and the like.

In the present invention, a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group is preferred. Thereby, the film forming property (suppression of cracking or warpage) and moisture resistance at the time of forming a cured film can be further improved. Specific examples thereof include polymers having the following repeating units. The polymer having the repeating unit described below is preferably a polymer having an epoxy group.

<<Compound having partial structure represented by 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 crosslinkage such as an unsaturated double bond, an epoxy group or an oxetane group. base.

(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 made into 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 may, for example, be 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 group containing the divalent linking group. The group of the combination.

Specific examples of such an organic group are preferably -OR', -SR', or a ring containing the group and -(CH ₂ ) _m - (m is an integer of 1 to 10) and having a carbon number of 5 to 10. a group of a combination of at least one of an alkyl group, -O-, -CO-, -COO-, and -NH-. Here, R' is preferably a hydrogen atom, a linear chain having a carbon number of 1 to 10, or a branched or cyclic alkyl group having a carbon number of 3 to 10 (preferably a linear or carbon number of 1 to 7 carbon atoms). a group of 3 to 7 branched or cyclic alkyl groups, 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 .

Further, in the formula (1), R ¹ and C may be bonded to each other to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is the nitrogen atom in the formula (1). The heterocyclic structure is preferably a 5-membered ring or a 6-membered ring structure, more preferably a 5-membered ring structure. The heterocyclic structure may also be a condensed ring, preferably a single ring.

Specific examples of the preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and -OR'(R' is a linear alkyl group having 1 to 5 carbon atoms) and -(CH ₂ ) _m a group in which (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), and R ¹ and C in the formula (1) are bonded to form a heterocyclic ring structure (preferably a 5-membered ring structure).

The compound having a partial structure represented by the formula (1) is preferably represented by (the main chain structure of the polymer - the partial structure of the formula (1) - R ¹ ), or by the partial structure of (A-formula (1)) -B) is indicated. Here, A is a linear chain having a carbon number of 1 to 10, a branch having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. Further, B is a group containing -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5) and a combination of a partial structure of the formula (1) and a polymerizable group.

In addition, 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).

[Chem. 21]

(In the formula (1-1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. In the formula (1-2), R ⁷ represents a hydrogen atom or a methyl group. In the formula (1-3), L ¹ represents a divalent linking group, and R ⁸ represents a hydrogen atom or an organic group. In the formula (1-4), L ² and L ³ each independently represent a divalent linking group, and R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an organic group. In the formula (1-5), L ⁴ represents a divalent linking group, and R ¹¹ to R ¹⁴ 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 has the same meaning as R ¹ in the formula (1), and the preferred range is also the same.

In the formula (1-3) to the formula (1-5), L ¹ to L ⁴ represent a divalent linking group. The divalent linking group preferably comprises -(CH ₂ ) _m - (m is an integer of 1 to 10), a cyclic alkyl group having 5 to 10 carbon atoms, -O-, -CO-, -COO- and - A combination of at least one of NH- is more preferably -(CH ₂ ) _m - (m is an integer of from 1 to 8).

In the formulae (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.

Alkyl groups can also be substituted. Further, the alkyl group may be in the form of a chain, a branch or a ring, and is preferably a linear or cyclic group. 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 further preferably an alkyl group having 1 to 6 carbon atoms.

Alkenyl groups can also be substituted. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 1 to 4 carbon atoms, and particularly preferably a vinyl group.

The substituent may, for example, be a polymerizable group, a halogen atom, an alkyl group, a carboxylate group, a halogenated alkyl group, an alkoxy group, a methacryloxy group, an acryloxy group, an ether group, a sulfonyl group, a thioether. Base, guanamine, sulfhydryl, hydroxy, carboxyl, and the like. Among these substituents, a polymerizable group (e.g., a vinyl group, a (meth) propylene fluorenyl group, a (meth) acryl fluorenyl group, an epoxy group, an aziridine group, etc.) is preferable, and a vinyl group is more preferable. .

Further, the compound having a partial structure represented by the formula (1) may be a monomer or a polymer, 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 the formula (1-2).

Further, in the case where the compound having the partial structure represented by the formula (1) is a polymer, it is preferred to contain the partial structure in the side chain of the polymer.

The molecular weight of the compound having a partial structure represented by the formula (1) is preferably from 50 to 1,000,000, more preferably from 500 to 500,000. By setting such a molecular weight, the effects of the present invention can be more effectively achieved.

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

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, a compound having a partial structure represented by the formula (1) is preferably a polyacrylamide.

Further, specific examples of the compound having a partial structure represented by the formula (1) include a water-soluble polymer, and preferred examples of the main chain structure include polyvinylpyrrolidone, poly(meth)acrylamide, and poly Indoleamine, polyurethane, polyurea. The water-soluble polymer may also be a copolymer, and the copolymer may also be a random copolymer.

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

The poly(meth) acrylamide may, for example, be a polymer or a copolymer of (meth) acrylamide. Specific examples of the acrylamide include acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N-benzyl propylene. Indoleamine, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-tolyl acrylamide, N-(hydroxyphenyl) acrylamide, N-(amine sulfonylphenyl) propylene Guanamine, N-(benzene Alkylsulfonyl) acrylamide, N-(methylsulfonyl) acrylamide, N,N-dimethyl decylamine, N-methyl-N-phenyl acrylamide, N-hydroxyl Base-N-methacrylamide and the like. Further, methacrylamide corresponding to the acrylamides can also be used in the same manner.

The water-soluble polyamine resin may, for example, be a compound obtained by copolymerizing a polyamine resin with a hydrophilic compound. The so-called water-soluble polyamide resin derivatives, for example, refers to a water-soluble polyamide resin as a raw material and Amides (-CONH-) linkages hydrogen atoms substituted with methoxymethyl (-CH ₂ OCH ₃₎ of A compound-like compound having a structural change in a guanamine bond by a substitution or addition reaction of an atom in a water-soluble polyamide resin molecule.

The polyamine resin may, for example, be a so-called "n-nylon" synthesized by polymerization of an ω-amino acid or a so-called "n, m-nylon" synthesized by copolymerization of a diamine and a dicarboxylic acid. Among them, from the viewpoint of imparting hydrophilicity, a copolymer of a diamine and a dicarboxylic acid is preferred, and a reaction product of ε-caprolactam and a dicarboxylic acid is more preferred.

Examples of the hydrophilic compound include a hydrophilic nitrogen-containing cyclic compound, a polyalkylene glycol, and the like.

Here, the hydrophilic nitrogen-containing cyclic compound means a compound having a tertiary amine component in a side chain or a main chain, and examples thereof include an aminoethyl piperazine, a bisaminopropyl piperazine, and an α-di Methylamino-ε-caprolactam and the like.

On the other hand, in the compound obtained by copolymerizing a polyamine resin with a hydrophilic compound, copolymerization on the main chain of the polyamide resin is, for example, selected from a hydrophilic nitrogen-containing cyclic compound and a polyalkylene glycol. At least one of the group consisting of N-methoxymethylated nylon, the polyamide bond of the polyamide resin has a greater hydrogen bonding ability.

Among the compounds obtained by copolymerizing a polyamine resin with a hydrophilic compound, 1) a reaction product of ε-caprolactam with a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid, and 2) ε-hexa The reaction product of endoamine and a polyalkylene glycol with a dicarboxylic acid.

These compounds are commercially available, for example, from Toray Finetech Co., Ltd. under the trademark "AQ Nylon". The reaction product of ε-caprolactam and a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid can be obtained as AQ nylon A-90 manufactured by Toray Finetech Co., Ltd., ε-caprolactam The reaction product with the polyalkylene glycol and the dicarboxylic acid can be obtained as AQ nylon P-70 manufactured by Toray Finetech Co., Ltd. AQ nylon A-90, AQ nylon P-70, AQ nylon P-95, and AQ nylon T-70 (manufactured by Toray Industries, Inc.) can be used.

The molar content of the polymer containing the repeating unit having the partial structure represented by the formula (1) and the repeating unit having an epoxy group is preferably from 10/90 to 90/10, more preferably from 30/70 to 70/. 30. The weight average molecular weight of the copolymer is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 200,000.

The details of the use of the polymerizable compound, such as the structure, the use alone or in combination, and the amount of addition, can be arbitrarily set according to the final performance design of the near-infrared absorbing composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. In addition, from the viewpoint of improving the strength of the near-infrared cut filter, it is preferable to use a trifunctional or higher functional group, and further, a combination of different functional groups and different polymerizable groups (for example, acrylate, methacrylate, styrene) Compound, vinyl ether compound) The method of both the sensitivity and the intensity is also effective. In addition, the compatibility and dispersibility of other components (for example, a metal oxide, a dye, and a polymerization initiator) contained in the near-infrared absorbing composition are important reasons for selecting and using a polymerizable compound. For example, compatibility may be improved by using a low-purity compound or a combination of two or more. Further, from the viewpoint of improving the adhesion to the hard surface of the support or the like, a specific structure may be selected.

The addition amount of the polymerizable compound in the composition of the present invention can be set to 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 1 mass, based on the total solid content other than the solvent. Range of %~10% by mass.

Further, when a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, the total solid content of the composition of the present invention excluding the solvent is preferably set to 10% by mass to 75 mass. %, more preferably 20% by mass to 65% by mass, and particularly preferably 20% by mass to 60% by mass.

The number of the polymerizable compounds may be one or two or more. When two or more types are used, the total amount is in the above range.

<Binder Polymer>

In the present invention, in order to improve film properties and the like, a binder polymer may be further contained as needed. An alkali-soluble resin can be used as the binder polymer.

The content of the alkali-soluble resin can be referred to in the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099; Incorporated into the specification of the present application.

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

<Surfactant>

The composition of the present invention may also contain a surfactant. The surfactant may be used alone or in combination of two or more. The amount of the surfactant added may be set to 0.0001% by mass to 2% by mass, or may be set to 0.005% by mass to 1.0% by mass, or may be set to 0.01% by mass to 0.1% by mass based on the solid content of the composition of the present invention. %.

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

In particular, since the composition of the present invention contains at least one of a fluorine-based surfactant and an anthrone-based surfactant, the solution characteristics (especially fluidity) in the preparation of the coating liquid are further improved, so that the coating can be further improved. The uniformity of the thickness of the cloth or the liquid-saving property.

In other words, when a film is formed by using a coating liquid (a composition containing at least one of a fluorine-based surfactant and an anthrone-based surfactant), the coated surface and the coating liquid are used. The interfacial tension is reduced, the wettability to the coated surface is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

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

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac R08 (above produced by Di Aisheng (DIC)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)), Surflon S-382, Surflon S-141, Surflon S-145, Suffolk Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Sha Fulong ( Surflon) SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass), F-top ) EF301, F-top EF303, F-top EF351 Aifo Extension (F-top) EF352 (as above Jiemu Ke (Jemco) () manufactured), PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA (OMNOVA) Co., Ltd.).

As the fluorine-based surfactant, a polymer having a fluoroaliphatic group can be used. The polymer having a fluoroaliphatic group can be exemplified by a fluorine-based surfactant having a fluoroaliphatic group, and the fluoroaliphatic group is polymerized by short-chain polymerization. A fluoroaliphatic compound produced by a telomerization method (also referred to as a short-chain polymer method) or an oligomerization method (also referred to as an oligomer method).

Here, the "short-chain polymerization method" refers to a method of synthesizing a compound having a low molecular weight substance and having one to two active groups in the molecule. In addition, the "low polymerization method" means a method of converting a monomer or a mixture of monomers into an oligomer.

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

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

The fluoroaliphatic group-containing polymer of the present invention may use the fluoroaliphatic group-containing monomer of the present invention and (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene))methyl group. Acrylate copolymer. The copolymer may be irregularly distributed or may be subjected to block copolymerization. Further, the poly(oxyalkylene) group may, for example, be a poly(oxyethylidene) group, a poly(oxypropyl) group, a poly(oxybutylene) group, or the like, or may be a poly(oxyethylidene) group. a block-bonding group of an oxygen-extended propyl group and an oxygen-extended ethyl group; or a polyalkylene group having a different chain length in the same chain length; General unit. Further, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate (or methacrylate) may be not only a bivalent copolymer but also two or more different types. Monomer having a fluoroaliphatic group or two or more (poly(oxyalkylene)) propylene A ternary or higher copolymer obtained by copolymerizing an acid ester (or methacrylate) or the like at the same time.

The commercially available surfactant containing the fluoroaliphatic group-containing polymer of the present invention is exemplified by paragraph 0552 of the Japanese Patent Laid-Open Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099 The surfactants described in the following) are incorporated into the specification of the present application. Further, using F-781 (Dainippon Ink & Chemicals (shares) manufactured) MEGA method (Megafac), an acrylate C ₆ F ₁₃ group (or methacrylate) with (poly (oxy ethyl elongation)) a copolymer of acrylate (or methacrylate) with (poly(oxypropyl)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₈ F ₁₇ group and a copolymer of poly(oxyalkylene))acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₈ F ₁₇ group and (poly(oxyethylidene)) acrylate ( Or a copolymer of (methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate).

Examples of the nonionic surfactant include polyoxyethylene ethyl ether, polyoxyethylene ethyl allylate, polyoxyethyl alcohol ester, sorbitan fatty acid ester, and polyoxyethylene A sorbitan fatty acid ester, a polyoxyethylene ethylamine, a glycerin fatty acid ester, an oxygen extended ethyloxy propyl block copolymer, an acetylene glycol surfactant, an acetylene polyoxyepoxide Ethane and the like. These compounds may be used alone or in combination of two or more.

Specific trade names can be listed as: Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Sophino (Surfynol) 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 104S, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol 504, Surfynol CT-111, Surfynol CT-121, Sophino ( Surfynol) CT-131, Surfynol CT-136, Surfynol CT-141, Surfynol CT-151, Surfynol CT-171, Sophino ( Surfynol) CT-324, Surfynol DF-37, Surfynol DF-58, Surfynol DF-75, Surfynol DF-110D, Sophino ( Surfynol) DF-210, Surfynol GA, Surfynol OP-340, Surfynol PSA-204, Surfynol PSA-216, Surfynol PSA-336, Surfynol SE, Surfynol SE-F, Surfynol TG, Surfynol GA, Dainol 604 (above is Nisshin Chemical (Air Products & Chemicals), Olfine A, Olfine B, Olfi Ne) AK-02, Olfine CT-151W, Olfine E1004, Olfine E1010, Olfine P, Olfine SPC, Orr Olfine STG, Olfine Y, Olfine 32W, Olfine PD-001, Olfine PD-002W, Olfine PD- 003, Olfine PD-004, Olfine EXP. 4001, Olfine EXP. 4036, Olfine EXP. 4051, Olfine AF- 103, Olfil AF-104, Olfine SK-14, Olfine AE-3 (above is Nisshin Chemical), Acetylenol E00, Acetylenol E13T, Acetylenol E40, Acetylenol E60, Acetylenol E81, Acetylenol E100, Acetylenol E200 (all above Product name, manufactured by Kawasaki Seiki Co., Ltd.). Among them, Olfine E1010 is preferred.

In addition, the nonionic surfactants described in JP-A-2012-208494, paragraph 0553 (corresponding to US Patent Application Publication No. 2012/0235099, [0679]), etc. These are incorporated into the specification of the present application.

Specific examples of the cation-based surfactant include the cationic surfactant described in paragraph 0554 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding US Patent Application Publication No. 2012/0235099 [0680]). The content is incorporated into the specification of the present application.

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

Examples of the fluorenone-based surfactants include an anthrone-based surfactant described in paragraph 0556 of the Japanese Patent Laid-Open Publication No. 2012-208494 (the corresponding Japanese Patent Application Laid-Open No. 2012/0235099, No. [0682]). This is incorporated into the specification of the present application. In addition, Toray Silicone (Toray Silicone) manufactured by Toray-Dow Corning Co., Ltd. can also be exemplified. SF8410", Toray Silicone SF8427, Toray Silicone SH8400, ST80PA, ST83PA, ST86PA, manufactured by Momentive Performance Materials "TSF-400", "TSF-401", "TSF-410", "TSF-4446", "KP321", "KP323", "KP324", "KP340" manufactured by Shin-Etsu Chemicals Co., Ltd.

<Polymerization initiator>

The composition of the present invention may also contain a polymerization initiator. The polymerization initiator may be used alone or in combination of two or more. 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 from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably from 0.1% by mass 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 light or heat, and may be appropriately selected depending on the intended purpose, and is preferably a photopolymerizable compound. In the case where polymerization is initiated by light, it is preferred to have a sensitivity to ultraviolet light to visible light.

Further, in the case where polymerization is initiated by heat, a polymerization initiator which decomposes at 150 ° C to 250 ° C is preferred.

The polymerization initiator which can be used in the invention is preferably a compound having at least an aromatic group, and examples thereof include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, and a benzophenone compound. A benzoin ether compound, a ketal derivative compound, a thioxanthone compound, an anthraquinone compound, a hexaarylbiimidazole compound, a trihalomethyl compound, an azo compound, an organic peroxide, a diazo compound, An onium compound such as an anthracene compound, an anthraquinone compound, an oxazine compound or a metallocene compound, an organic boron salt compound, a diterpene compound or the like.

From the viewpoint of sensitivity, a hydrazine compound, an acetophenone-based compound, an α-amino ketone compound, a trihalogenated methyl compound, a hexaarylbiimidazole compound, and a thiol compound are preferable.

The acetophenone-based compound, the trihalogenated methyl compound, the hexaarylbiimidazole compound, and the hydrazine compound can be specifically referred to the paragraphs 0506 to 0510 of the Japanese Patent Laid-Open Publication No. 2012-208494 (corresponding U.S. Patent Application Publication No. 2012/0235099 The contents of the specification [0622 to 0628] and the like are incorporated in the specification of the present application.

The photopolymerization initiator is more preferably a compound selected from the group consisting of an anthraquinone compound, an acetophenone-based compound, and a mercaptophosphine compound. More specifically, for example, an amino acetophenone-based initiator described in JP-A-10-291969, and a mercaptophosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. Further, the oxime-based initiators described above and the oxime-based initiators may be those described in JP-A-2001-233842.

As the ruthenium compound, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) can be used as a commercial product. Acetophenone-based initiators can be used as commercially available products such as IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names; all of which are BASF Japan) Japan) manufactured by the company). In addition, a mercaptophosphine-based initiator can be used as a commercially available product. (IRGACURE)-819 or DAROCUR-TPO (trade name; all manufactured by BASF Japan).

<Other ingredients>

In the composition of the present invention, in addition to the essential component or the additive, other components may be appropriately selected depending on the purpose as long as the effects of the present invention are not impaired.

Examples of other components which can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like, and further may be used in combination. Adhesion promoter and other auxiliary agents on the surface of the substrate (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer) Agent, etc.).

By appropriately containing these components, properties such as stability and film physical properties of the target near-infrared absorption filter can be adjusted.

For example, Japanese Patent Application Publication No. 2008-250074 can be referred to in the following paragraphs 0183 of the specification of the Japanese Patent Application Publication No. 2013/0034812. The descriptions of paragraph number 0101 to paragraph number 0102, paragraph number 0103 to paragraph number 0104, and paragraph number 0107 to paragraph number 0109 of the publication are incorporated in the specification of the present application.

Since the composition of the present invention can be made into a liquid form, for example, by directly coating the composition of the present invention and drying it, a near-infrared cut filter can be easily produced, and the conventional near-infrared cut filter can be improved. Full manufacturing suitability.

In the near-infrared cut filter of the present invention, the rate of change of the absorbance ratio obtained by the following formula before and after heating at 200 ° C for 5 minutes is preferably 7% or less, more preferably 5% or less, and further preferably 2%. the following.

[(Absorbance ratio before heating - Ratio of absorbance after heating) / Absorbance ratio before heating]

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

Further, the near-infrared cut filter of the present invention preferably has a rate of change of the absorbance ratio obtained by the following formula of 7% or less before and after being left at a high temperature and high humidity of 85 ° C / 95% relative humidity for 3 hours, respectively. More preferably, it is 5% or less, and further preferably 2% or less.

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

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

The film thickness of the near-infrared cut filter of the present invention is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 1 μm to 500 μm, more preferably 1 μm to 300 μm, still more preferably 1 μm to 200 μm. In the present invention, even in the case of producing such a film, high near-infrared ray blocking properties can be maintained.

The use of the near infrared ray absorbing composition of the present invention is not particularly limited, and examples thereof include a near-infrared cut filter for receiving light on the solid-state image sensor substrate (for example, a near-infrared cut filter for a wafer level lens, etc.) The near-infrared cut filter for the back side of the solid-state image sensor substrate (the side opposite to the light-receiving side) is preferably a light-shielding film on the light-receiving side of the solid-state image sensor substrate. In particular, the near-infrared absorbing composition of the present invention is applied directly to an image sensor for a solid-state imaging device to form a coating film.

In particular, the near-infrared ray absorbing composition of the present invention preferably has a structure containing a copper compound and a formula (1), and has a near-infrared cut filter having a film thickness of 200 μm or less and a visible light transmittance of 90% or more.

In addition, in the case of forming an infrared cut-off layer by coating, the viscosity of the near-infrared absorbing composition of the present invention is preferably 1 mPa. Above s, 3000mPa. Within the range of s below, more preferably 10mPa. Above s, 2000mPa. s the following range, and then preferably 100mPa. Above s, 1500mPa. s the following range.

When the near-infrared ray absorbing composition of the present invention is a near-infrared cut-off filter on the light-receiving side of the solid-state image sensor substrate and is formed by coating to form an infrared cut-off layer, thick film formability and uniform coatability are obtained. In view of view, the viscosity is preferably at 10 mPa. Above s, 3000mPa. Within the range of s below, more preferably 500mPa. Above s, 1500mPa. The range below s, the best is 700mPa. Above s, 1400mPa. s the following range.

The total solid content of the near-infrared absorbing composition of the present invention is changed depending on the coating method, and is preferably 1% by mass to 50% by mass, more preferably 1% by mass based on the composition. %~30% by mass, and further preferably 10% by mass to 30% by mass.

The present invention can also be formed into a laminate having a near-infrared cut-off layer and a dielectric multilayer film obtained by curing the near-infrared absorbing composition. For example, (i) a transparent support, a near-infrared cut-off layer, and a dielectric multilayer film are sequentially provided, and (ii) a near-infrared cut-off layer, a transparent support, and a dielectric multilayer film are sequentially disposed. kind. The transparent support may be a glass substrate, and a transparent resin substrate may also be mentioned.

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

As the material of the dielectric multilayer film, for example, ceramic can be used. Alternatively, it is also possible to use a noble metal film having absorption in the near-infrared range in consideration of the thickness and the number of layers without affecting the transmittance of visible light of the near-infrared cut filter.

Specifically, the dielectric multilayer film can be preferably formed by alternately laminating a high refractive index material layer and a low refractive index material layer.

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 in the range of usually 1.7 to 2.5 is selected.

Examples of the material include titanium oxide (titanium dioxide), zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide, and indium oxide, or a small amount of these oxides as a main component. Titanium oxide, tin oxide and/or antimony oxide. Among these materials, titanium oxide (titanium dioxide) is preferred.

As the 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 in the range of usually 1.2 to 1.6 is selected.

Examples of the material include cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride. Among these materials, cerium oxide is preferred.

The thickness of each of the high refractive index material layer and the low refractive index material layer is usually a thickness of 0.1 λ to 0.5 λ of the infrared wavelength λ (nm) to be blocked. When the thickness is outside the above range, the product of the refractive index (n) and the film thickness (d) (n × d) is greatly different from the optical film thickness calculated by λ/4, and the optical characteristics of reflection and refraction are related. Destruction has a tendency to control the blocking and transmission of specific wavelengths.

Further, the number of layers of the dielectric multilayer film is preferably from 5 to 50 layers, more preferably from 10 to 45 layers.

Furthermore, the present invention also relates to a method for fabricating a near-infrared cut filter, comprising the steps of: applying to a light-receiving side of a solid-state imaging device substrate (preferably coating or printing, more preferably applicator coating). a near-infrared absorbing composition, thereby forming a film; and a step of drying. The film thickness, the laminate structure, and the like can be appropriately selected depending on the purpose.

The support may be a transparent substrate including glass or the like, or may be a solid-state imaging device substrate, or may be another substrate (for example, a glass substrate 30 to be described later) provided on the light-receiving side of the solid-state imaging device substrate, or may be provided on the solid-state imaging device. A layer such as a flattening layer on the light receiving side of the substrate.

The method of applying the near-infrared absorbing composition (coating liquid) to the support can be applied, for example, by using a spin coater, a slit spin coater, a slit coater, screen printing, or applicator coating. Wait until implementation.

In addition, the drying conditions of the coating film depend on the type of each component, the solvent, and the ratio of use. It is usually dried at a temperature of 60 ° C to 200 ° C for 30 seconds to 15 minutes.

The method of forming the near-infrared cut filter using the near-infrared absorbing composition of the present invention may also include other steps. The other steps are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a surface treatment step of the substrate, a pre-heating step (pre-baking step), a hardening treatment step, a post-heating step (post-baking step), and the like.

<Preheating step, post heating step>

The heating temperature in the pre-heating step and the post-heating step is usually from 80 ° C to 200 ° C, preferably from 90 ° C to 180 ° C.

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

<hardening treatment step>

The hardening treatment step is a step of hardening the formed film as needed, and by performing this treatment, the mechanical strength of the near-infrared cut filter is improved.

The hardening treatment step is not particularly limited and may be appropriately selected depending on the purpose, and for example, a total exposure treatment, a total heat treatment, or the like can be preferably exemplified. Here, the term "exposure" as used in the present invention is intended to include not only irradiation of light of various wavelengths but also radiation irradiation of an electron beam or X-rays.

The exposure is preferably performed by irradiation of radiation, and ultraviolet rays or visible light such as an electron beam, KrF, ArF, g-ray, h-ray, or i-ray may be preferably used, particularly for radiation that can be used for exposure. Preferably, KrF, g-ray, h-ray, and i-ray are preferred.

The exposure method may be a stepper exposure or an exposure using a high pressure mercury lamp.

The exposure amount is preferably ⁵ mJ/cm ² to 3000 mJ/cm ² , more preferably 10 mJ/cm ² to 2000 mJ/cm ² , and particularly preferably 50 mJ/cm ² to 1000 mJ/cm ² .

The method of the full exposure treatment may, for example, be 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 hardening of the polymer component in the film formed by the composition is promoted by the overall exposure, the hardening of the film is further progressed, and the mechanical strength and durability are maintained. Sex has been improved.

The apparatus for performing full exposure is not particularly limited and may be appropriately selected depending on the purpose. For example, an ultraviolet (UV) exposure machine such as an ultrahigh pressure mercury lamp can be preferably used.

Further, the method of the overall heat treatment may be a method of heating the entire surface of the formed film. The film strength of the pattern can be increased by full heating.

The heating temperature for the overall heating is preferably from 120 ° C to 250 ° C, more preferably from 120 ° C to 250 ° C. When the heating temperature is 120° C. or more, the film strength is improved by heat treatment, and when the heating temperature is 250° C. or lower, the components in the film are prevented from being decomposed and the film quality is weakened and become brittle.

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

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

Further, the present invention relates to a camera module including a solid-state imaging device substrate and a near-infrared cut filter disposed on a light receiving side of the solid-state imaging device substrate, and the near-infrared cut filter is the present invention Near-infrared cut-off filter.

Hereinafter, a camera module according to an embodiment of the present invention will be described with reference to Figs. 2 and 3, but the present invention is not limited to the following specific examples.

In addition, in FIGS. 2 and 3, common parts are denoted by common symbols.

In addition, in the description, "upper", "upper" and "upper side" refer to the side away from the substrate 10, and "lower", "lower" and "lower side" refer to the side closer to the substrate 10 .

2 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image sensor.

The camera module 200 shown in FIG. 2 is connected to the circuit board 70 as a mounting substrate via a solder ball 60 as a connection member.

Specifically, the camera module 200 is configured to include a solid-state imaging device substrate 100 including an imaging element portion on the first main surface of the substrate, and a first main surface side of the solid-state imaging device substrate 100 (light receiving) a planarization layer (not shown in FIG. 3), a near-infrared cut filter 42 provided on the planarization layer, and a lens disposed above the near-infrared cut filter 42 and having the imaging lens 40 in the internal space The holder 50 and the light shielding and electromagnetic shield cover 44 that are disposed to surround the periphery of the solid-state imaging device substrate 100 and the glass substrate 30 are provided. Further, a glass substrate 30 (light-transmitting substrate) may be provided on the planarization layer. Each member is bonded by an adhesive 45.

The present invention also relates to a method of manufacturing a camera module, comprising: a camera module having a solid-state imaging device substrate 100 and a near-infrared cut filter 42 disposed on a light receiving side of the solid-state imaging device substrate, and In the method of manufacturing a camera module, the near-infrared absorbing composition of the present invention is applied to the light-receiving side of the solid-state image sensor substrate to form a film. In the camera module of the present embodiment, for example, the near-infrared absorbing composition of the present invention is applied onto a flattening layer to form a film, and a near-infrared cut filter 42 can be formed. The method of coating the near-infrared cut filter is as described above.

In the camera module 200, the incident light hν from the outside passes through the imaging lens 40, the near-infrared cut filter 42, the glass substrate 30, and the planarization layer in order, and reaches the imaging element portion of the solid-state imaging device substrate 100.

The camera module 200 is provided with a near-infrared cut filter directly on the flattening layer, or a flattening layer may be omitted, and a near-infrared cut filter may be directly disposed on the microlens, and a near-infrared cut filter may be disposed on the glass substrate 30. A glass substrate 30 provided with a near-infrared cut filter can also be attached.

FIG. 3 is a cross-sectional view showing the solid-state imaging element substrate 100 in FIG. 2 enlarged.

The solid-state imaging device substrate 100 includes an imaging element 12, an interlayer insulating film 13, a matrix layer 14, a color filter 15, an overcoat layer 16, and a microlens 17 in this order on the first main surface of the substrate 10 as a substrate. The red color filter 15R, the green color filter 15G, and the blue color filter 15B are disposed so as to correspond to the image sensor 12 (hereinafter, these are collectively referred to as "color filter". Sheet 15") or microlens 17. On the second main surface of the tantalum substrate 10 opposite to the first main surface, The light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are provided. Each member is bonded by the adhesive 20.

The microlens 17 is provided with a planarization layer 46 and a near-infrared cut filter 42. Instead of the planarization layer, a near-infrared cut filter may be provided on the microlens 17, between the matrix layer 14 and the color filter 15, or between the color filter 15 and the overcoat layer 16. A near-infrared cut filter 42 is provided on the 46. More preferably, it is disposed at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. When it is set at this position, the step of forming the near-infrared cut filter can be simplified, and the near-infrared rays which are unnecessary for the microlens can be sufficiently cut off, so that the near-infrared ray blocking property can be further improved.

For the solid-state imaging device substrate 100, reference may be made to the description of the solid-state imaging device substrate 100 after paragraph 0255 of the Japanese Patent Application Laid-Open No. 2012-068418 (the corresponding Japanese Patent Application Publication No. 2012/068292 (the [0407]). This content is incorporated into the specification of the present application.

Although an embodiment of the camera module has been described above with reference to FIGS. 2 and 3, the above-described embodiment is not limited to the embodiment of FIGS. 2 and 3.

[Examples]

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

<Synthesis Example> <Synthesis of Polymer (A1)> <<Synthesis of Polymer A-1>>

5.0 g of polyether oxime (manufactured by BASF Co., Ltd., Ultrason E6020P) 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 reacting for 48 hours at room temperature, the reaction liquid was added dropwise to 1 L of a hexane/ethyl acetate (1/1) mixture which was cooled in ice water. The supernatant was removed, and the resulting precipitate was dissolved in methanol. The obtained solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was collected by filtration. The obtained solid was dried under reduced pressure, whereby 4.9 g of polymer A-1 was obtained. The sulfonic acid group content (meq/g) in the polymer was calculated by neutralization titration. The weight average molecular weight (Mw) was determined by gel permeation chromatography.

<<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 70 ° C for 7 hours.

[Chem. 24]

<<Synthesis of Polymer A-3>>

Polymer A-3 was obtained in the same manner as in the synthesis of 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.

<<Synthesis of Polymer A-4>>

8.0 g of polyfluorene (manufactured by Aldrich Co., Ltd.) 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. After reacting at room temperature for 1 hour, a solid precipitated. The supernatant was removed, and the obtained solid was washed with chloroform and dissolved in methanol. This solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was collected by filtration. The obtained solid was dried under reduced pressure, whereby 8.3 g of polymer A-4 was obtained.

[Chem. 26]

<<Synthesis of Polymer A-5>>

In a three-necked flask equipped with a Dean-Stark tube, hexafluorobisphenol A 3.42 g, diphenylphosphonium-4,4'-dichloro-3,3'-disulfonic acid was added. Sodium 5.00 g, potassium carbonate 1.69 g, toluene 10 g, and N-methylpyrrolidone 25 g were refluxed for 4 hours under a nitrogen stream. After the toluene in the system was removed, the temperature was raised to 180 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama funnel covered with diatomaceous earth, and the filtrate was added dropwise to 300 ml of saturated brine. The obtained precipitate was filtered, dissolved in methanol, and added dropwise to 500 ml of acetone. The obtained precipitate was filtered, dissolved in methanol, and subjected to salt exchange to a proton type by Amberlyst 15 (hydrogen foam) (manufactured by Aldrich Co., Ltd.), whereby 6.4 g of polymer A-5 was obtained.

<<Synthesis of Polymer A-6>>

Changed 3.42g of hexafluorobisphenol A to 1.22g of hydroquinone, in addition to Synthesis of Compound A-5 gave 3.9 g of polymer A-6 in the same manner.

<<Synthesis of Polymer A-7>>

In a three-necked flask equipped with a Dean-Stark tube, 4.66 g of diphenolic acid, 8.00 g of disodium diphenylphosphonium-4,4'-dichloro-3,3'-disulfonate, and potassium carbonate 2.48 were added. g, 10 g of toluene and 25 g of N-methylpyrrolidone were refluxed for 4 hours under a nitrogen stream. After the toluene in the system was removed, the temperature was raised to 180 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama funnel covered with diatomaceous earth, and the filtrate was added dropwise to 300 ml of saturated brine. The obtained precipitate was filtered, dissolved in methanol, and added dropwise to 500 ml of acetone. The obtained 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 reacting for 6 hours at room temperature, the reaction liquid was added dropwise to 1.5 L of a hexane/ethyl acetate (1/1) mixture which was cooled in ice water. The supernatant was removed, and the resulting precipitate was dissolved in methanol. The obtained solution was added dropwise to 0.5 L of ethyl acetate, and the obtained precipitate was collected by filtration. The obtained solid was dried under reduced pressure, whereby 7.5 g of polymer A-7 was obtained.

<<Synthesis of Polymer A-8>>

Add 4,4'-biphenol 3.53g, benzophenone-4,4'-difluoro-3,3'-disulfonic acid disodium 8.00g to a three-necked flask equipped with a Dean-Stark tube 3.10 g of potassium carbonate, 10 g of toluene, and 30 g of dimethyl hydrazine were refluxed for 4 hours under a nitrogen stream. After the toluene in the system was removed, the temperature was raised to 170 ° C and stirred for 15 hours. After the reaction solution was returned to room temperature, the reaction solution was filtered through a Kiriyama funnel covered with diatomaceous earth, and the filtrate was added dropwise to 500 ml of saturated brine. The obtained precipitate was filtered, dissolved in methanol, and added dropwise to 800 ml of acetone. The obtained precipitate was filtered, dissolved in methanol, and subjected to salt exchange to a proton type by Amberlyst 15 (hydrogen foam) (manufactured by Aldrich Co., Ltd.), whereby 7.2 g of polymer A-8 was obtained.

<<Synthesis of Polymer A-9>>

Sulfonation of polyetheretherketone is carried out according to the method described in "J. Membr. Sci." (229, 2004, 95-106), thereby obtaining polymer A-9.

<<Synthesis of Polymer A-10>>

The sulfonation of polyphenylene ether is carried out according to the method described in "Chinese J. Polym. Sci." (20, No. 1, 2002, 53-57), thereby obtaining polymer A- 10.

<<Synthesis of Polymer A-11>>

According to the second embodiment of the Japanese Patent Laid-Open Publication No. 2008-533225 Method Obtaining Polymer A-11.

<<Synthesis of Polymer A-12>>

The sulfomethylation of the polyfluorene is carried out according to the method described in JP-A-2004-131662, whereby the polymer A-12 is obtained.

<<Synthesis of Polymer A-13>>

The polymer A-13 was obtained by the method described in Japanese Patent Laid-Open Publication No. 2008-27890.

[化35]

<<Synthesis of Polymer A-14>>

To the 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 mixture was stirred under a nitrogen stream until the solution became homogeneous. To the 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 ° C for 4 hours, followed by reaction at 180 ° C for 20 hours. After the reaction temperature was returned to room temperature, the reaction liquid was added to acetone. The obtained precipitate was filtered, dissolved in methanol, and then subjected to salt exchange to a proton type by Amberlyst 15 (hydrogen foam) (manufactured by Aldrich Co., Ltd.), whereby 9.2 g of polymer A-14 was obtained.

<<Synthesis of Polymer A-15>>

The sulfomethylation of the polyfluorene was carried out according to the method described in "J. Membr. Sci." (360, 2010, 26-33), whereby the polymer A-15 was obtained.

[化37]

<Synthesis of copper complexes> <<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 copper hydroxide. By the above operation, an aqueous solution of a copper complex (hereinafter also referred to as an engineering plastic copper complex) Cu-1 was obtained.

<<Synthesis of copper complex Cu-2~ copper complex Cu-17>>

The copper complex Cu-2~copper was synthesized in the same manner as the synthesis of the copper complex Cu-1 except that the mass ratio of the acid group of the polymer A1 to the equivalent of the copper atom was set as shown in the following Table 1. Compound Cu-17.

<<Synthesis of copper complex Cu-18>>

3.00 g of ethanesulfonic acid and 3.76 g of butanesulfonic acid were diluted into 100 ml of methanol, and 2.66 g of copper hydroxide was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction liquid was concentrated, and the obtained solid was dried under reduced pressure, whereby a copper compound Cu-18 was obtained.

<<Synthesis of copper complex Cu-19>>

6.00 g of ethanesulfonic acid was diluted into 100 ml of methanol, and 2.66 g of copper hydroxide was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction liquid was concentrated, and the obtained solid was dried under reduced pressure, whereby a copper compound Cu-19 was obtained.

<<Synthesis of copper complex Cu-20>>

Adding 1.84 g of copper acetate to 20 g of a 20% aqueous solution of polymer A-3 at room temperature Stir under 3 hours. The reaction liquid was concentrated by an evaporator, and after the produced acetic acid was removed, water was added thereto to prepare a 20% aqueous solution again, thereby obtaining an aqueous solution of the copper complex Cu-20.

<<Synthesis of copper complex Cu-21 (Comparative Synthesis Example 1)>>

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

<Preparation of Near Infrared Absorbing Composition> <<Example 1>> <Preparation of Near Infrared Absorbing Composition 1>

The near-infrared absorbing composition of Examples 1 to 21 and Comparative Example 1 was prepared by mixing a copper complex and a solvent so as to have a compounding amount shown in Table 2 below.

Further, the copper complex Cu-22 in the following Table 2 was copper (II) fluorohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent EG was ethylene glycol (Wako Pure Chemical Industries, Ltd.). Manufactured by the Industrial Co., Ltd., the solvent MeOH is methanol (manufactured by Wako Pure Chemical Industries, Ltd.).

<<Making of near infrared cutoff filter>>

The near-infrared absorbing composition prepared in the examples and the comparative examples was respectively used by an applicator coating method (a Baker applicator manufactured by YOSHIMITSU SEIKI and a YBA-3 type adjusted to have a slit width of 250 μm). Dressing applied to On the glass substrate, preheating (prebaking) was performed at 100 ° C for 120 seconds. Thereafter, all the samples were heated at 180 ° C for 180 seconds using a hot plate to obtain a near-infrared cut filter.

<evaluation> <<Near infrared shielding evaluation>>

The transmittance of the near-infrared cut filter obtained as described above at a wavelength of 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-technologies Co., Ltd.). The near-infrared shielding property was evaluated according to the following criteria.

A: Transmittance at a wavelength of 800 nm ≦ 5%

B: 5% < transmittance at a wavelength of 800 nm ≦ 7%

C: 7% <wavelength at 800 nm ≦ 10%

D: 10% < transmittance at a wavelength of 800 nm

<<Water resistance evaluation>>

The near-infrared cut filter obtained as described above was allowed to stand under high temperature and high humidity of 85 ° C / 95% relative humidity for 3 hours. Before the moisture resistance test and the moisture resistance test, the maximum absorbance of the near-infrared cut filter wavelength of 700 nm to 1400 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-technologies Co., Ltd.). The absorbance ratio expressed by "Absλmax/Absλmin" was obtained by Absλmax) and the minimum absorbance (Absλmin) of the wavelength of 400 nm to 700 nm. The absorbance ratio expressed by the ratio (absorbance ratio before the test - the absorbance ratio after the test) / the absorbance ratio before the test × 100 | (%) was evaluated according to the following criteria Rate of change.

A: Absorbance ratio change rate ≦2%

B: 2% < absorbance ratio change rate ≦ 4%

C: 4% < absorbance ratio change rate ≦ 7%

D: 7% < absorbance ratio change rate

<<Heat resistance evaluation 1>>

The near-infrared cut filter obtained as described above was allowed to stand at 200 ° C for 5 minutes. Before the heat resistance test and the heat resistance test, the maximum absorbance (Absλmax) of the near-infrared cut filter at a wavelength of 700 nm to 1400 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Co., Ltd.). And the minimum absorbance (Absλmin) at a wavelength of 400 nm to 700 nm, and the absorbance ratio expressed by "Absλmax/Absλmin" was obtained.

The absorbance ratio change rate indicated by ((absorbance ratio before test - absorbance ratio after test) / absorbance ratio before test) × 100 | (%) was evaluated according to the following criteria. The results are shown in Table 3 below.

A: Absorbance ratio change rate ≦2%

B: 2% < absorbance ratio change rate ≦ 4%

C: 4% < absorbance ratio change rate ≦ 7%

D: 7% < absorbance ratio change rate

<<Heat resistance evaluation 2>>

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

As shown in the above Table 3, when the near-infrared absorbing composition of the example is formed into a cured film, a cured film which maintains high near-infrared ray shielding property and is excellent in heat resistance can be formed. Further, the near-infrared absorbing composition of the example can form a cured film excellent in moisture resistance.

On the other hand, the near-infrared absorbing composition of the comparative example was inferior in heat resistance when it was made into a cured film, compared with the Example. In addition, the near infrared absorption of the comparative example The composition of the composition was inferior in moisture resistance when it was made into a cured film as compared with the examples.

<<Example 23>> <<Preparation of near-infrared absorbing composition>>

The following components were mixed in the amounts shown in the following Table 4 to prepare a 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 adhesive A

. Surfactant A described below

. Solvent (water)

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

Surfactant A: Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.)

Copper complex A was synthesized as follows.

A 53.1% aqueous solution of sulfophthalic acid (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and the solution was heated to 50 ° C, then copper hydroxide (2.84 g, 29.1 mmol) was added and reacted at 50 ° C 2 hour. After completion of the reaction, the solvent and the produced water were distilled off by an evaporator, whereby copper complex A (8.57 g) was obtained.

<<Example 24 to Example 37>>

In the near-infrared absorbing composition of Example 23, the engineering plastic copper complex Cu-2~ engineering plastic copper complex Cu-15 was used instead of the engineering plastic copper complex Cu-1, respectively. In the same manner as in Example 23, the near-infrared absorbing compositions of Examples 24 to 37 were prepared in the same manner.

With respect to the near-infrared absorbing composition of Examples 23 to 37, it was confirmed that the near-infrared absorbing ability can be further improved.

1‧‧‧Compounds containing acid-based ions (A2) and copper ions

2‧‧‧Copper ion

3‧‧‧Main chain

4‧‧‧ side chain

5‧‧‧ Acid-based ion sites

Claims (17)

A near-infrared absorbing composition comprising a compound obtained by reacting a polymer (A1) with a copper component, wherein the polymer (A1) has an aromatic hydrocarbon group and/or an aromatic heterocyclic group in a main chain, It also contains an acid group or a salt thereof. The near-infrared absorbing composition according to claim 1, wherein the polymer (A1) contains a structural unit represented by the following formula (A1-1); 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 near-infrared absorbing composition according to claim 1 or 2, wherein the polymer (A1) contains a structural unit represented by the following formula (A1-2); In the formula (A1-2), Ar ² represents an aromatic hydrocarbon group and/or an aromatic heterocyclic group, Y ² represents a single bond or a divalent linking group, X ² represents an acid group or a salt thereof, and 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; and R ³ represents a hydrogen atom or a hydrocarbon group. The near-infrared absorbing composition according to claim 2, wherein the divalent linking group represents a linear, branched or cyclic alkyl group, an aryl group, -O-, -S- , -C(=O)-, -C(=O)O-, or a group comprising such combinations. The near-infrared absorbing composition according to claim 1 or 2, wherein the acid group or a salt thereof is selected from the group consisting of a carboxylic acid group and a salt thereof, a phosphate group and a salt thereof, a phosphonic acid group, and a salt, and at least one of a sulfonic acid group and a salt thereof. The near-infrared absorbing composition according to claim 1 or 2, wherein the acid group or a salt thereof is at least one selected from the group consisting of a carboxylic acid group and a salt thereof, and a sulfonic acid group and a salt thereof. . The near-infrared absorbing composition according to claim 1 or 2, wherein the polymer (A1) has a weight average molecular weight of 1,000 to 10,000,000. The near-infrared absorbing composition according to claim 1 or 2, further comprising water. A near-infrared absorbing composition containing a copper complex compound having a polymer (A2) having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain and containing an acid group ion The acid-based ion site serves as a ligand. A near-infrared absorbing composition comprising: an aromatic hydrocarbon group and/or an aromatic heterocyclic group in a main chain, and an acid group or a compound obtained by reacting a salt polymer (A1) and a copper component; and a copper complex obtained by a reaction of a low molecular compound containing an acid group or a salt thereof and a copper component. The near-infrared absorbing composition according to claim 10, wherein the molecular weight of the low molecular compound is 1000 or less. The near-infrared absorbing composition according to claim 10, wherein the low molecular compound contains at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom. A near-infrared cut filter obtained by using the near-infrared absorbing composition according to any one of claims 1 to 12. The near-infrared cut filter according to claim 13, wherein the rate of change of the absorbance ratio obtained by the following formula before and after heating at 200 ° C for 5 minutes is 5% or less; [(before heating) Absorbance ratio - absorbance ratio after heating / absorbance ratio before heating] The absorbance ratio refers to a value obtained by dividing the maximum absorbance at a wavelength of 700 nm to 1400 nm by the minimum absorbance at a wavelength of 400 nm to 700 nm. A method of manufacturing a near-infrared cut filter, comprising the step of: coating a near-infrared absorbing composition according to any one of claims 1 to 12, on a light-receiving side of a solid-state image sensor substrate, Thereby a film is formed. A camera module including a solid-state imaging element substrate and a near-infrared cut filter disposed on a light receiving side of the solid-state imaging device substrate, and the near-infrared cut filter is as in claim 13 or 14 The near-infrared cut filter described in the item. A method of manufacturing a camera module, comprising: a camera module having a solid-state image sensor substrate and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor substrate, and a method of manufacturing the camera module includes the following In the step of coating the near-infrared absorbing composition according to any one of the first to twelfth aspects of the invention, the film is formed on the light-receiving side of the solid-state image sensor substrate.