TW201602322A - Method for adjusting spectral of near infrared absorptive material, near infrared absorptive composition, near infrared cut filter and method for manufacturing near infrared cut filter, camera module, and spectral adjusting agent of copper compound - Google Patents

Abstract

The invention provides a method for adjusting spectrum of a near infrared absorptive material which is able to obtain a high near infrared shielding ability and desired spectral characteristic, a near infrared absorptive composition and a method for manufacturing the same, a near infrared cut filter and a method for manufacturing the same, a camera module, and a spectrum adjusting agent of a copper compound. The method for adjusting spectral of the near infrared absorptive material includes a step of mixing the spectral adjusting agent in the copper compound. The spectral adjusting agent of the copper compound includes a compound (A1) having one or more coordinating atom which is coordinated with a non-shared electron pair, or a compound (A2) having at least 2 coordination sites.

Description

Spectral adjustment method for near-infrared absorbing material, near-infrared absorption Receptive composition, near-infrared cut filter, manufacturing method thereof, camera module, and spectroscopic adjusting agent for copper compound

The present invention relates to a spectroscopic adjustment method for a near-infrared absorbing material, a near-infrared absorbing composition, a near-infrared cut filter, a method for producing the same, a camera module, and a spectroscopic adjusting agent for a copper compound.

In a video camera, a digital still camera, a mobile phone with a camera function, etc., a charge-coupled device (CCD) or a complementary type of a solid-state imaging element as a color image is used. Metal oxide semiconductor (Complementary Metal-Oxide-Semiconductor, CMOS). In these solid-state imaging devices, a silicon photodiode having sensitivity to near-infrared rays is used in the light-receiving portion. Therefore, it is necessary to perform visual sensitivity correction, and a near-infrared cut filter is often used.

As a material of such a near-infrared cut filter, a near-infrared absorbing composition using a copper sulfonate complex (Patent Document 1) or a near-infrared absorbing composition using a copper phosphate complex is also known. (Patent Document 2).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-213918

[Patent Document 2] International Publication WO1999/010354 Manual (Japanese Patent No. 3933392)

Here, in the case where a copper compound is used as a material for forming a near-infrared cut filter, it is required to improve the near-infrared shielding ability and obtain desired spectral characteristics.

An object of the present invention is to solve the above problems, and an object of the invention is to provide a spectroscopic adjustment method for a near-infrared absorbing material which can obtain a high near-infrared shielding ability and a required spectral characteristic when a cured film is formed. Further, an object of the present invention is to provide a near-infrared absorbing composition capable of obtaining high near-infrared shielding ability and required spectral characteristics when a cured film is formed, a near-infrared cut filter, a method of manufacturing the same, and a camera module . Further, an object of the present invention is to provide a spectroscopic adjusting agent for a copper compound which can adjust the spectroscopicity of a copper compound to obtain a high near-infrared shielding ability.

The inventors of the present invention conducted intensive studies based on the above-described conditions, and as a result, found that the problem can be solved by blending a spectroscopic adjusting agent with a copper compound.

Specifically, the above problem is solved by the following means <1>, preferably means <2> to means <15>.

<1> A spectroscopic adjustment method of a near-infrared absorbing material, comprising the step of formulating a spectroscopic modifier in a copper compound.

(2) The spectroscopic adjustment method of the near-infrared absorbing material according to the above, wherein the spectroscopic adjusting agent contains a compound (A1) having one or more coordinating atoms coordinated by a non-covalent electron pair, or Compound (A2) having at least two coordination sites.

<3> The spectroscopic adjustment method of a near-infrared absorbing material according to <1>, wherein the spectroscopic modifier has at least one coordination site coordinated by an anion and is coordinated with a non-covalent electron pair a compound (A2-1) having a coordinating atom, a compound (A2-2) having two or more coordinating atoms coordinated by a non-covalent electron pair, or a compound having two monoanionic coordination sites (A2-3).

The spectroscopic adjustment method of the near-infrared absorbing material according to any one of <1> to <3> wherein the spectroscopic adjusting agent has a pKa of 0.5 to 32.

The spectroscopic adjustment method of the near-infrared absorbing material according to any one of the above-mentioned, wherein the spectroscopic adjusting agent contains one or more coordination positions coordinated by a non-covalent electron pair. a compound of an atom, a copper atom in a copper compound, and a non-covalent electron in a spectroscopic modifier The molar ratio of the coordination atoms of the row coordination is copper atom: coordination atom = 1: 0.1 to 1: 4.0.

The spectroscopic adjustment method of the near-infrared absorbing material according to any one of <1> to <5> wherein the copper compound contains a polymer copper complex.

<7> A near-infrared absorbing composition comprising a copper compound and a spectroscopic modifier.

<8> The near-infrared absorbing composition according to <7>, wherein the spectral modifier has a pKa of 0.5 to 32.

<9> The near-infrared absorbing composition according to <7> or <8>, wherein the spectroscopic adjusting agent contains a compound having one or more coordinating atoms coordinated by a non-covalent electron pair, and a copper compound The copper atom and the molar ratio of the coordination atom coordinated by the non-covalent electron pair in the spectroscopic modifier are copper atoms: coordination atom = 1: 0.1 to 1: 4.0.

The near-infrared absorbing composition according to any one of <7> to <9> wherein the copper compound comprises a polymer copper complex.

<11> The near-infrared absorbing composition according to any one of <7> to <10> further comprising a curable compound and a solvent.

<12> A near-infrared ray-cutting filter which is obtained by curing the near-infrared absorbing composition according to any one of <7> to <11>.

<13> A method for producing a near-infrared-cut filter, comprising: coating a near-infrared absorbing composition according to any one of <7> to <11> on a light-receiving side of a solid-state image sensor, thereby forming a film step.

<14> A camera module having a solid-state imaging element and being disposed in a solid a near-infrared cut filter that is light-receiving on the light-receiving side of the image sensor, and a near-infrared cut filter that hardens the near-infrared absorbing composition according to any one of <7> to <11> .

<15> A spectroscopic adjusting agent for a copper compound, comprising: a compound (A1) having one or more coordinating atoms coordinated by a non-covalent electron pair, or a compound having at least two coordination sites (A2) .

According to the present invention, it is possible to provide a spectroscopic adjustment method of a near-infrared absorbing material which can obtain high near-infrared shielding ability and desired spectral characteristics. Further, it is possible to provide a near-infrared absorbing composition, a near-infrared cut filter, a method for producing the same, and a camera module which can obtain high near-infrared shielding ability and desired spectral characteristics when a cured film is formed. Further, it is possible to provide a spectroscopic modifier of a copper compound which can adjust the spectroscopicity of a copper compound to obtain a high near-infrared shielding ability.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧Lens mount

16‧‧‧Photographic Components Division

17‧‧‧Color Filter

18‧‧‧Microlens

19‧‧‧UV. Infrared light reflecting film

20‧‧‧Transparent substrate

21‧‧‧Near infrared absorption layer

22‧‧‧Anti-reflective layer

1 is a schematic cross-sectional view showing a configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.

2 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module.

3 is a schematic cross-sectional view showing an example of a peripheral portion of a near-infrared cut filter in a camera module.

4 is a view showing a peripheral portion of a near-infrared cut filter in a camera module. A schematic cross-sectional view of an example.

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

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

In the expression of the group (atomic group) in the specification of the present application, it is not described that the substituted and unsubstituted expression includes a group having no substituent (atomic group), and also contains a group having a substituent (atomic group). . For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the specification of the present application, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means acrylonitrile group. And methacryl oxime.

In addition, in the specification of the present application, "single quantity" and "monomer" have the same meaning. The singly is a compound which is different from the oligomer and the polymer and has a weight average molecular weight of 2,000 or less.

In the specification of the present application, the polymerizable compound means a compound having a polymerizable functional group, and may be a single amount or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

The method for measuring the weight average molecular weight and the number average molecular weight of the compound used in the present invention can be measured by gel permeation chromatography (GPC) and measured by GPC. Ethylene conversion value is defined. For example, the weight average molecular weight and the number average molecular weight can be determined by using HLC-8220 (manufactured by Tosoh Co., Ltd.) and manufactured using TSKgel Super AWM-H (Tosoh). 6.0 mm ID × 15.0 cm) was used as a column, and a 10 mmol/L lithium bromide N-methyl pyrrolidinone (NMP) solution was used as a solution.

The near-infrared ray refers to light (electromagnetic wave) having a maximum absorption wavelength in the range of 700 nm to 2500 nm.

In the specification of the present application, the term "total solid content" means the total mass of the components obtained by removing the solvent from the total composition of the composition. The solid component in the present invention is a solid component at 25 °C.

<Spectral adjustment method>

The spectroscopic adjustment method of the near-infrared absorbing material of the present invention comprises the step of formulating a spectroscopic adjusting agent in a copper compound.

According to the present invention, it is possible to achieve both high heat resistance and good spectral characteristics when the cured film is formed. Although the mechanism is not determined, the spectroscopic adjusting agent used in the present invention deforms the structure of the copper compound as an infrared absorbing material and improves the spectral characteristics. Therefore, it can be considered that a high near-infrared shielding ability can be obtained.

<<Copper compound>>

The copper compound used in the present invention is a substance having infrared absorbing property. Specifically, a copper compound having a maximum absorption wavelength in a wavelength range of 700 nm to 1000 nm (near infrared ray range) is preferred. Further, even if the copper compound itself does not have infrared absorbing properties, the spectrally adjusted compound has infrared absorbing properties. The situation is also included in the present invention.

The copper in the copper compound used in the present invention is preferably monovalent copper or divalent copper, more preferably divalent copper. Further, the copper content in the copper compound used in the present invention is preferably from 2% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass. By increasing the content of the copper compound, the near-infrared shielding ability can be improved. In the case where two or more kinds of copper compounds are used, it is preferred that the total amount thereof is within the above range.

The copper compound used in the present invention may be a copper compound other than the copper complex, or may be a copper complex, preferably a copper complex. As the copper compound, 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 more preferably copper acetate, copper chloride, copper formate, copper hydroxide, copper stearate, copper benzoate, copper ethyl acetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate. , copper sulfate, copper carbonate, copper chlorate, copper (meth)acrylate, copper perchlorate, and thus preferably copper acetate, copper chloride, copper sulfate, copper hydroxide, copper benzoate, copper (meth)acrylate . The copper salt is preferably a monovalent copper salt or a divalent copper salt, more preferably a divalent copper salt.

In the present invention, a copper compound obtained by reacting a compound having an acid group with a copper component is more preferable, and a compound containing at least one of a sulfonic acid group, a carboxylic acid group, a phosphinic acid group, and a phosphoric acid group is more preferably used. A copper compound obtained by reacting a copper component (hereinafter, these compounds may be referred to as a copper sulfonate compound, a copper carboxylate compound, a copper phosphinate compound, or a copper phosphate compound), and further preferably a copper sulfonate compound or a carboxylic acid. The copper compound and the copper phosphate compound are more preferably a copper sulfonate compound or a copper carboxylate compound.

Further, the copper compound may be a low molecule or a polymer. The details will be described below.

(low molecular type)

The copper compound used in the present invention is preferably represented by the following formula (i).

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

In the formula (i), 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.

In the case where the copper compound is a copper complex, it is a form in which the ligand is disposed on the copper of the center metal. The copper in the copper complex used in the present invention is divalent copper, and can be obtained, for example, by mixing or reacting a compound which is a ligand or a salt thereof with a copper component. Therefore, in the case of "infrared absorbing composition containing copper and a ligand", a copper complex can be expected to be formed in the composition.

The compound to be a ligand is preferably a compound having a coordination site, and is preferably a compound represented by the following formula (ii).

(In the formula (ii), X ¹ represents a coordination site, n3 represents an integer of 1 to 6, and R ¹ represents a single bond or an n-valent group)

In the formula (ii), X ^{1 is} preferably a coordination site coordinated by an anion or a coordination site coordinated by a non-covalent electron pair. The coordination site to which the anion is coordinated is exemplified by a monoanionic coordination site described later and a coordination site coordinated by an anion described later. The monoanionic coordination site and the coordination site coordinated by an anion have the same meanings as the monoanionic coordination site described later and the coordination site coordinated by an anion, and the preferred range is also the same. The coordination site coordinated by the non-covalent electron pair is preferably a ring containing a coordinating atom coordinated by a non-covalent electron pair described later or a partial structure selected from a group (UE) to be described later.

X ¹ may also be an acid group, and is preferably at least one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom. X ¹ may be used alone or in combination of two or more, preferably two or more, and preferably contains a sulfonic acid group and a carboxylic acid group.

In the formula (ii), n3 is preferably from 1 to 3, more preferably 2 or 3, and still more preferably 3.

In the formula (ii), the n-valent group is preferably an n-valent organic group or an n-valent organic group and -O-, -SO-, -SO ₂ -, -NR ^N1 -, -CO-, a group of -CS- groups. Examples of the n-valent organic group include a hydrocarbon group, an oxygen alkyl group, a heterocyclic group and the like. Further, the n-valent group may be a group containing at least one selected from the group (AN-1) described later, a ring containing a coordinating atom coordinated by a non-covalent electron pair described later, or a selected one. A group derived from at least one of the groups (UE-1) described later.

The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, a halogen atom (preferably a fluorine atom), and a polymerizable group (e.g., a vinyl group, a (meth) acrylonitrile group, an epoxy group, and an oxetane group. Base, etc.), sulfonic acid group, carboxylic acid group, acid group containing phosphorus atom, carboxylate group (for example, -CO ₂ CH ₃ ), hydroxyl group, alkoxy group (for example, methoxy group), amine group, amine formazan a group, an amine methyl methoxy group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group), a (meth) acryloxy group, or the like. When the hydrocarbon group has a substituent, the substituent may be further substituted, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.

In the case where the hydrocarbon group is monovalent, it is preferably an alkyl group, an alkenyl 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. When the hydrocarbon group is trivalent or higher, it is preferably a group corresponding to the monovalent hydrocarbon group or the divalent hydrocarbon group.

The alkyl group and the alkylene group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the linear alkyl group and the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and still more preferably from 1 to 8. The carbon number of the branched alkyl group and the alkylene group is preferably from 3 to 20, more preferably from 3 to 12, and still more preferably from 3 to 8. The cyclic alkyl group and the alkylene group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group and the alkylene group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10.

The number of carbon atoms of the alkenyl group and the alkenyl group is preferably from 2 to 10, more preferably from 2 to 8, more preferably from 2 to 4.

The carbon number of the aryl group and the aryl group is preferably from 6 to 18, more preferably from 6 to 14, more preferably from 6 to 10.

The heterocyclic group may be a group having a hetero atom or an aromatic heterocyclic group in the alicyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. In addition, the heterocyclic group is monocyclic or condensed. The ring is preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring having a condensation number of 2 to 4. The heterocyclic group may have a substituent, and the substituent has the same meaning as the substituent which the above-mentioned hydrocarbon group may have.

In the case of -NR ^N1 -, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and has the same meaning as R ^N1 in the compound (A2-3) described later.

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

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 more, more preferably 80 or more, and the upper limit is preferably 750 or less, more preferably 600 or less.

Copper sulfonate complex (copper sulfonate compound)

The copper sulfonate complex used in the present invention is a compound having copper as a central metal and a sulfonic acid compound as a ligand.

The sulfonic acid compound is more preferably a compound represented by the following formula (iii).

(In the formula (iii), R ² represents a monovalent organic group)

The sulfonic acid represented by the formula (iii) and a salt thereof function as a ligand to be coordinated to copper.

Specific examples of the specific monovalent organic group of R ² in the formula (iii) include a hydrocarbon group, and specific examples thereof include a linear, branched or cyclic alkyl group, an alkenyl group, an aryl group and the like. The groups may also be a divalent linking group (for example, a linear or branched alkyl group, a cyclic alkyl group, an aryl group, -O-, -S-, -CO-, - A group of COO-, -OCO-, -SO ₂ -, -NR- (R is a hydrogen atom or an alkyl group).

The carbon number of the linear alkyl group, the branched alkyl group, the cyclic alkyl group, the alkenyl group and the aryl group has the same meaning as the description in R ¹ in the above formula (ii), The range is also the same.

The monovalent organic group may have a substituent, and the substituent may be a substituent which R ¹ in the above formula (ii) may have. The substituent which the linear alkyl group and the branched alkyl group may have is at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. The substituent which the aryl group may have is exemplified by at least one of an alkyl group, an alkoxy group, a halogenated alkyl group, a halogen atom, a polymerizable group, a sulfonic acid group, a carboxylic acid group and a methyl carboxylate group, preferably a sulfonic acid group. At least one of a group and a carboxylic acid group.

The linear or branched alkylene group, the cyclic alkylene group, and the extended aryl group as the divalent linking group may, for example, be a linear, branched or cyclic alkyl group or a aryl group as described above. The obtained divalent linking group is derivatized by removing one hydrogen atom from the group.

The molecular weight of the compound represented by the formula (iii) is preferably from 80 to 750, more preferably from 80 to 600, and still more preferably from 80 to 450.

Further, the copper sulfonate complex of the present invention contains a structure represented by the following formula (iv).

[Chemical 3]

(In the formula (iv), R ³ represents a monovalent organic group. "*" means a site which forms a coordinate bond with copper)

In the formula (iv), R ³ has the same meaning as R ² in the formula (iii), and the preferred range is also the same.

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

[Chemical 4]

[Chemical 5]

[Chemical 6]

The copper sulfonate complex compound used in the present invention can be obtained by reacting a sulfonic acid compound which is a ligand or a salt thereof with a copper component.

As the copper component, 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. The copper salt is more preferably copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate, Copper carbonate, copper chlorate, copper (meth)acrylate, copper perchlorate, and further preferably copper acetate, copper chloride, copper sulfate, copper benzoate, copper (meth)acrylate.

The sulfonic acid compound used in the present invention may be a commercially available sulfonic acid, or may be referred to as a public Know the method to synthesize. The salt of the sulfonic acid compound is preferably a metal salt, and specific examples thereof include a sodium salt and a potassium salt.

The reaction ratio when the copper component is reacted with the sulfonic acid compound or a salt thereof as described above is preferably set to be 1:1.5 to 1:4 in terms of a molar ratio. In this case, the sulfonic acid compound or a salt thereof may be used alone or in combination of two or more.

Further, the reaction conditions when the copper component is reacted with the above-described sulfonic acid compound or a salt thereof are preferably set to, for example, 20 ° C to 50 ° C for 0.5 hours or longer.

The maximum absorption wavelength and gram absorbance of the copper sulfonate complex of the present invention have the same meanings as the phosphorus-containing copper complex described above, and the preferred range is also the same.

In addition to the compound, a copper compound using a carboxylic acid as a ligand can also be used as the copper compound used in the present invention. Furthermore, the invention is not limited thereto. The carboxylic acid used in the copper compound having a carboxylic acid as a ligand is, for example, preferably a compound represented by the following formula (v).

(In the formula (v), R ⁴ represents a monovalent organic group)

In the formula (v), R ⁴ represents a monovalent organic group. The monovalent organic group is not particularly limited, and has the same meaning as the monovalent organic group R ² in the above formula (iii), and the preferred range thereof is also the same.

The copper compound used in the present invention can also be used as a coordination with a phosphate ester. Copper compound (copper phosphate compound). The phosphate compound used in the copper phosphate compound can be referred to the specification of the present application by referring to paragraphs 0015 to 0027 of Japanese Patent Laid-Open Publication No. 2013-253224.

(polymer type)

As the copper compound used in the present invention, a polymer copper complex can also be used. The heat resistance can be improved by the copper compound containing a polymer copper complex.

The polymer copper complex is a polymer type copper compound containing a polymer containing an acid group ion site and a copper ion, and preferably a polymer type having a acid group ion site in the polymer as a ligand. Copper compound. The polymer type copper compound usually has an acid group ion site in a side chain of the polymer, an acid group ion site is bonded to copper (for example, a coordinate bond is formed), and a crosslinked structure is formed between the side chains with copper as a starting point. . The polymer type copper complex compound may be a copper complex of a polymer having a carbon-carbon bond in the main chain, a copper complex of a polymer having a carbon-carbon bond in the main chain, and containing fluorine. A copper complex of an atom, a copper complex of a polymer having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain (hereinafter referred to as an aromatic group-containing polymer), and the like.

The copper component is preferably a compound containing divalent copper. The copper content in the copper component is preferably from 2% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass. The copper component may be used alone or in combination of two or more. As the copper-containing compound, for example, copper oxide or a copper salt can be used. The copper salt is more preferably divalent copper. Copper salts are particularly preferably copper hydroxide, copper acetate and copper sulfate.

The acid group of the polymer containing an acid group or a salt thereof is not particularly limited as long as it can react with the copper component described above, and it is preferred to form a coordinate bond with the copper component. With The acid group having an acid dissociation constant (pKa) of 12 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 acid group or the like is preferable. The acid groups may be one type or two or more types.

The atom or 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. Further, in the polymer containing an acid group or a salt thereof, the acid group or a salt thereof may be contained in at least one of the main chain and the side chain, and is preferably contained in at least one side chain.

The polymer containing an acid group or a salt thereof is preferably a polymer containing a carboxylic acid group or a salt thereof and/or a sulfonic acid group or a salt thereof, and more preferably a polymer containing a sulfonic acid group or a salt thereof.

<<<The first polymer containing an acid group or a salt thereof>>

A preferred example of the polymer containing an acid group or a salt thereof has a structure in which a main chain has a carbon-carbon bond, and preferably contains a structural unit represented by the following formula (A1-1).

(In the formula (A1-1), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a single bond or a divalent linking group, and M ¹ represents a hydrogen atom or an atom or a group which forms a salt with a sulfonic acid group)

In the formula (A1-1), R ^{1 is} preferably a hydrogen atom.

In the case of the formula (A1-1), when L ¹ represents a divalent linking group, the divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group, a heteroaryl group, and -O-, -S. -, -CO-, -COO-, -OCO-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group containing a combination of these groups.

The divalent hydrocarbon group may, for example, be a linear or branched or cyclic alkyl group or an extended aryl group. The hydrocarbon group may also have a substituent, preferably unsubstituted.

The carbon number of the linear alkyl group is preferably from 1 to 30, more preferably from 1 to 15, more preferably from 1 to 6. Further, the carbon number of the branched alkyl group is preferably from 3 to 30, more preferably from 3 to 15, more preferably from 3 to 6.

The cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10.

The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 14, more preferably from 6 to 10, and particularly preferably a phenyl group.

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

In the formula (A1-1), the atom or atom group represented by M ¹ and the sulfonic acid group-constituting salt has the same meaning as the atom or atom group of the salt constituting the acid group described above, preferably a hydrogen atom or Alkali metal atom.

Other constituent units other than the constituent unit represented by the formula (A1-1) can be referred to the paragraph number 0068 to paragraph number 0075 of the Japanese Patent Laid-Open Publication No. 2010-106268 (corresponding U.S. Patent Application Publication No. 2011/0124824). The description of the copolymerized components disclosed in 0112]~[0118]) is incorporated into the specification of the present application.

The other constituent unit which is preferable is a structural unit represented by the following formula (A1-2).

In the formula (A1-2), R ³ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Y ² represents a single bond or a divalent linking group, and the divalent linking group has the same meaning as the divalent linking group of the above formula (A1). In particular, Y ^{2 is} preferably -COO-, -CO-, -NH-, a linear or branched alkylene group, or a group containing a combination of such groups, or a single bond.

In the formula (A1-2), X ² represents -PO ₃ H, -PO ₃ H ₂ , -OH or -COOH, preferably -COOH.

In the case where the polymer (A1-1) contains another constituent unit (preferably, the constituent unit represented by the formula (A1-2)), the constituent unit represented by the formula (A1-1) The moieties of the constituent units represented by the formula (A1-2) are preferably from 95:5 to 20:80, more preferably from 90:10 to 40:60.

<<<The second polymer containing an acid group or a salt thereof>>

The copper compound which can be used in the present invention may also be a polymer having an acid group or a salt thereof and having an aromatic hydrocarbon group and/or an aromatic heterocyclic group in the main chain (hereinafter referred to as a A polymer-based copper compound obtained by reacting an aromatic group polymer with a copper component. The aromatic group-containing polymer 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 acid group or the salt thereof and the copper component are the same as those of the copper compound obtained by the reaction of the polymer containing the acid group or the salt thereof and the copper component described above, and the preferred range is also the same.

The aromatic hydrocarbon group is preferably, for example, an aryl group. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and more preferably from 6 to 12. Especially preferred is phenyl, naphthyl or biphenyl. 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, for example, be a nitrogen atom, an oxygen atom or a sulfur atom, preferably nitrogen or oxygen.

When the aromatic hydrocarbon group and/or the aromatic heterocyclic group has a substituent T, the substituent T may, for example, be an alkyl group or a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond) or 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 sulfonyl group, a thioether group Amidino group, mercapto group, hydroxyl group, carboxyl group, aralkyl group or the like is preferably an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms).

The aromatic group-containing polymer is particularly preferably at least one polymer selected from the group consisting of a polyether oxime polymer, a polyfluorene polymer, a polyether ketone polymer, and a polyphenylene ether polymer. Polyimine-based polymer, polybenzimidazole-based polymer, polyphenyl-based polymer, phenol resin-based polymer, polycarbonate-based polymer, and polyamine-based polymer Combination and polyester based polymer. Examples of the respective polymers are shown below.

Polyether oxime 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-based 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-)

For example, the polyether oxime polymer, the polyfluorene polymer, and the polyether ketone 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 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.

A preferred example of the aromatic group-containing polymer preferably contains a structural unit represented by the following formula (A1-3).

(In the formula (A1-3), 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)

In the case of the formula (A1-3), when Ar ¹ represents an aromatic hydrocarbon group, it has the same meaning as the above-mentioned aromatic hydrocarbon group, and the preferred range is also the same. When Ar ¹ represents an aromatic heterocyclic group, it has the same meaning as the above-mentioned aromatic heterocyclic group, and the preferred range is also the same.

Ar ¹ may have a substituent other than -Y ¹ -X ^{1 in the} above formula (A1-3). In the case where Ar ¹ has a substituent, the substituent has the same meaning as the substituent T described above, and the preferred range is also the same.

In the formula (A1-3), Y ^{1 is} preferably a single bond. In the case where Y ¹ represents 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 of combinations of such groups. Here, R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

The hydrocarbon group may, for example, be a linear, branched or cyclic alkylene or aryl group. The carbon number of the linear alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6. The carbon number of the branched alkyl group is preferably from 3 to 20, more preferably from 3 to 10, and still more preferably from 3 to 6. The cyclic alkyl group may be either a single ring or a polycyclic ring. The carbon number of the cyclic alkyl group is preferably from 3 to 20, more preferably from 4 to 10, and still more preferably from 6 to 10. With respect to the linear, branched or cyclic alkyl groups, the hydrogen atom in the alkyl group may be substituted by a fluorine atom.

The aryl group has the same meaning as the case where the divalent linking group of the formula (A1-1) described above is an exoaryl 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 the formula (A1-3), the acid group represented by X ¹ or a salt thereof has the same meaning as the above-mentioned acid group or a salt thereof, and the preferred range is also the same.

The weight average molecular weight of the polymer containing the constituent unit represented by the formula (A1-1), the formula (A1-2) or the formula (A1-3) is preferably 1,000 or more, more preferably from 1,000 to 10,000,000, and further preferably 3000~1 million, especially 4,000~400,000.

Containing the structure represented by formula (A1-1), formula (A1-2) or formula (A1-3) Specific examples of the unit-forming polymer include the following compounds and salts of the following compounds, but are not limited to these specific examples.

<<Specifying light adjuster>>

The spectroscopic modifier used in the present invention serves to increase the near-infrared shielding ability of the copper compound and to adjust the spectroscopic light. The spectroscopic adjusting agent is not particularly limited, and examples thereof include a compound (A1) having one or more coordinating atoms coordinated by a non-covalent electron pair (hereinafter also referred to as a compound (A1)), and having at least two coordination positions. Part Compound (A2) (hereinafter also referred to as compound (A2)), a compound having at least one coordination site coordinated by an anion and a coordination atom coordinated by a non-covalent electron pair (A2- 1) A compound (A2-2) having two or more coordination atoms coordinated by a non-covalent electron pair, and a compound (A2-3) having two monoanionic coordination sites.

The spectroscopic adjusting agent preferably has a molar absorption coefficient of the copper compound before blending the spectroscopic adjusting agent at the maximum absorption wavelength (λ _max ) and a molar absorption coefficient of the copper compound after blending the spectroscopic adjusting agent (mixing the spectroscopic adjusting agent) The molar absorption coefficient of the subsequent copper compound - the molar absorption coefficient of the copper compound before the preparation of the spectroscopic modifier is preferably more than 0.2 L / (mol. cm), more preferably 0.3 L / (mol. cm) or more. Further preferably, it is 0.4 L/(mol.cm) or more.

The pKa of the spectroscopic modifier is preferably from 0.5 to 32, more preferably from 0.5 to 20. By setting the pKa within the above range, stabilization of copper ions can be achieved more efficiently. Further, in the present invention, pKa basically means a pKa in water at 25 °C. The measurement that cannot be measured in water refers to a pKa obtained by changing the solvent suitable for measurement and measuring it. Specifically, the pKa described in "Chemical Fact Sheet" or the like can be referred to.

<Compound (A1)>

The compound (A1) may have one or more coordinating atoms coordinated by a non-covalent electron pair in the molecule, and may have two or more, preferably one to four, and more preferably have 1~3.

In the compound (A1), the coordinating atom coordinated by the non-covalent electron pair is preferably an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom or A sulfur atom, and thus preferably a nitrogen atom.

In the case of the compound (A1), when the coordinating atom coordinated by the non-covalent electron pair is a nitrogen atom, the atom adjacent to the nitrogen atom is a carbon atom, and it is preferred that the carbon atom has a substituent.

The coordinating atom coordinated by the non-covalent electron pair is preferably contained in the ring or contained in at least one partial structure selected from the group consisting of (UE).

(In the group (UE), R and R ¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom, an alkyl group, an alkenyl group, Alkynyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, amine or sulfhydryl)

In the case where a coordinating atom coordinated by a non-covalent electron pair is contained in a ring, the ring containing a coordinating atom coordinated by a non-covalent electron pair may be a single ring or a polycyclic ring, and It can be aromatic or non-aromatic. The ring containing a coordinating atom coordinated by a non-covalent electron pair is preferably a 5-membered ring to a 12-membered ring, more preferably 5 member ring ~ 7 member ring.

The ring containing a coordinating atom coordinated by a non-covalent electron pair may have a substituent, and examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and a carbon number of 6~. An aryl group, a halogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, a mercapto group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a carboxyl group.

In the case where the ring containing a coordinating atom coordinated by a non-covalent electron pair has a substituent, it may have a more substituent, and may include a coordinating atom containing a coordinate group coordinated by a non-covalent electron. a group of a ring, a group containing at least one partial structure selected from the group (UE), an alkyl group having 1 to 12 carbon atoms, a fluorenyl group having 2 to 12 carbon atoms, and a hydroxyl group.

In the case where a coordinating atom coordinated by a non-covalent electron pair is contained in a partial structure represented by a group (UE), R and R ¹ preferably each independently represent a hydrogen atom, an alkyl group, or an alkenyl group. , alkynyl, aryl or heteroaryl.

The alkyl group may also be linear, branched or cyclic, preferably linear. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4. An example of the alkyl group is a methyl group. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be a monocyclic ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, more preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. In the case where the alkyl group has a substituent, it may have a more substituent.

The alkenyl group and the alkynyl group have the same meanings as the alkenyl group and the alkynyl group described in the coordination site which is coordinated with an anion described later, and the preferred range is also the same.

The aryl group may be a single ring or a polycyclic ring, preferably a single ring. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6.

The heteroaryl group may be a single ring or a polycyclic ring. The number of the hetero atoms constituting the heteroaryl group is preferably from 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The carbon number of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12.

In the case where a coordinating atom coordinated by a non-covalent electron pair is contained in a partial structure represented by a group (UE), R ² preferably independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkyne. Alkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkylthio, arylthio, heteroarylthio, amine or fluorenyl.

The alkyl group has the same meaning as the alkyl group described in the group (UE), and the preferred range is also the same.

The number of carbon atoms of the alkenyl group is preferably from 1 to 10, more preferably from 1 to 6.

The alkynyl group preferably has a carbon number of from 1 to 10, more preferably from 1 to 6.

The aryl group has the same meaning as the aryl group described in the group (UE), and the preferred range is also the same.

The heteroaryl group has the same meaning as the heteroaryl group described in the group (UE), and the preferred range is also the same.

The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 3 to 9 carbon atoms.

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

The heteroaryloxy group may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroaryloxy group has the same meaning as the heteroaryl group described in the group (UE), and the preferred range is also the same.

The carbon number of the alkylthio group is preferably from 1 to 12, more preferably from 1 to 9.

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

The heteroarylthio group may be a single ring or a polycyclic ring. The heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described in the group (UE), and the preferred range is also the same.

The carbon number of the fluorenyl group is preferably from 2 to 12, more preferably from 2 to 9.

The compound having one or more coordinating atoms coordinated by a non-covalent electron pair is also preferably a compound having a 5-membered ring or a 6-membered ring, and is preferably a complex having a covalent electron pair. The atomic atoms constitute a 5-membered ring or a 6-membered ring.

It is also preferred that the coordinating atom which is coordinated by the non-covalent electron pair of the compound (A1) is a nitrogen atom. Further, it is also preferred that the atom adjacent to the nitrogen atom of the coordinating atom coordinated by the non-covalent electron pair of the compound (A1) is a carbon atom, and the carbon atom has a substituent. By setting such a configuration, the structure of the copper complex is more easily deformed, so that the color value can be further increased. The substituent may have the same meaning as the substituent having a coordinating atom coordinated by a non-covalent electron pair, and is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. And a carboxyl group, an alkoxy group having 1 to 12 carbon atoms, a fluorenyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a halogen atom.

The compound (A1) may have a coordination site coordinated by an anion in the molecule or may have no coordination site coordinated by an anion. Here, examples of the coordination site coordinated by an anion include a coordination site containing an oxyanion, a nitrogen anion, or a sulfur anion. The details will be described in the following compound (A2).

Specific examples of the compound (A1) include the following compounds, but are not limited thereto. These compounds.

<compound (A2)>

Specific examples of the compound (A2) include compounds having at least one coordination site coordinated by an anion and a coordination atom coordinated by a non-covalent electron pair (hereinafter also referred to as a compound (A2-) 1)) a compound having two or more coordination atoms coordinated by a non-covalent electron pair in one molecule (hereinafter also referred to as a compound (A2-2)), and having two monoanionic coordination sites A compound (hereinafter also referred to as a compound (A2-3)) or the like.

<<Compound (A2-1)>>

The compound (A2-1) has at least one coordination site coordinated by an anion in the molecule, and may have two. The compound (A2-1) may be two or more, as long as the coordination site coordinated by the anion in the molecule and the coordination atom coordinated by the non-covalent electron pair are two or more. It is 4. The compound (A2-1) may be used alone or in combination of two or more.

The form in which the coordination site coordinated by an anion is combined with the number of coordination atoms coordinated by a non-covalent electron pair is exemplified by having two anions coordinated. a coordination site with one coordinating atom coordinated by a non-covalent electron pair, a coordination site having one anion coordination, and two coordination sites coordinated by a non-covalent electron pair The situation of the atom.

The form of the coordination site coordinated by an anion and the number of coordination atoms coordinated by a non-covalent electron pair are four, and there are two coordination sites having two anions for coordination and two non-co-locations. In the case of a coordinating atom in which a valence electron pair is coordinated, a coordinating site in which one anion is coordinated and three coordinating atoms coordinated in a non-covalent electron pair.

In the compound (A2-1), the number of atoms constituting the anion of the coordination site coordinated by the anion and the coordination atom coordinated by the non-covalent electron pair is preferably from 1 to 6, more preferably 1~3. By setting such a configuration, the structure of the copper complex is more easily deformed, so that the color value can be further increased.

The anion which constitutes the coordination site coordinated by the anion and the atom which is coordinated by the coordination atom coordinated by the non-covalent electron pair may be one type or two or more types. The anion which constitutes the coordination site coordinated by the anion and the atom which is bonded to the coordination atom coordinated by the non-covalent electron pair are preferably carbon atoms.

In the following exemplified compounds, an anion constituting a coordination site coordinated by an anion is an oxyanion, and a coordination atom coordinated by a non-covalent electron pair is a nitrogen atom, and a coordination site constituting an anion is formed. The anion and the atom bonded to the coordinating atom coordinated by the non-covalent electron pair are carbon atoms. Further, the number of atoms constituting the anion of the coordination site coordinated by the anion and the coordination atom coordinated by the non-covalent electron pair is 2.

The molecular weight of the compound (A2-1) is preferably from 50 to 1,000, more preferably from 50 to 600.

In the compound (A2-1), the anion constituting the coordination site coordinated by the anion may be provided on the copper atom in the copper component, and is preferably an oxyanion, a nitrogen anion or a sulfur anion.

The coordination site coordinated by the anion is preferably at least one selected from the group consisting of the following groups (AN).

In the coordination site coordinated by the anion, X preferably represents N or CR, and R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

The alkyl group may be linear, branched or cyclic, and is preferably linear. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 1 to 4. Examples of alkyl groups can be listed Take methyl. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be a monocyclic ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, more preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. In the case where the alkyl group has a substituent, it may have a more substituent.

The number of carbon atoms of the alkenyl group is preferably from 1 to 10, more preferably from 1 to 6.

The alkynyl group preferably has a carbon number of from 1 to 10, more preferably from 1 to 6.

The aryl group may be a single ring or a polycyclic ring, preferably a single ring. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12, and still more preferably 6.

The heteroaryl group may be a single ring or a polycyclic ring. The number of the hetero atoms constituting the heteroaryl group is preferably from 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The carbon number of the heteroaryl group is preferably from 6 to 18, more preferably from 6 to 12.

In the compound (A2-1), a coordinating atom coordinated by a non-covalent electron pair has the same meaning as the compound (A1), and the preferred range is also the same.

The compound (A2-1) is also preferably represented by the following formula (IV).

X ¹ -L ¹ -Y ¹ Formula (IV)

(In the general formula (IV), X ¹ represents a coordination site represented by a group (AN). Y ¹ represents a ring or a group (UE) containing a coordination atom coordinated by a non-covalent electron pair. Partial structure represented. L ¹ represents a single bond or a divalent linking group)

In the general formula (IV), X ¹ has the same meaning as the coordination site coordinated by the anion, and the preferred range is also the same.

In the formula (IV), the partial structure of Y ¹ with the ring containing a coordinating atom coordinated by a non-covalent electron pair or the coordinate atom containing a coordinating atom with a non-covalent electron pair is The same meaning, the preferred range is also the same.

In the general formula (IV), when L ¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -O-, -SO ₂ - or a group containing a combination of such groups, more preferably an alkylene group having a carbon number of 1 to 3, a phenyl group or a -SO ₂ - group.

More specific examples of the compound (A2-1) include the compounds represented by the following formula (IV-1) to formula (IV-8).

X ² -L ² -Y ² -L ³ -X ³ (IV-1)

Y ³ -L ⁴ -Y ⁴ -L ⁵ -X ⁴ (IV-2)

Y ⁵ -L ⁶ -X ⁵ -L ⁷ -X ⁶ (IV-3)

Y ⁶ -L ⁷ -X ⁷ -L ⁸ -Y ⁷ (IV-4)

X ⁸ -L ⁹ -Y ⁸ -L ¹⁰ -Y ⁹ -L ¹¹ -X ⁹ (IV-5)

X ⁹ -L ¹² -Y ¹⁰ -L ¹³ -Y ¹¹ -L ¹⁴ -Y ¹² (IV-6)

Y ¹³ -L ¹⁵ -X ¹⁰ -L ¹⁶ -X ¹¹ -L ¹⁷ -Y ¹⁴ (IV-7)

Y ¹⁵ -L ¹⁸ -X ¹² -L ¹⁹ -Y ¹⁶ -L ²⁰ -Y ¹⁷ (IV-8)

In the general formulae (IV-1) to (IV-8), X ² to X ⁴ , X ⁸ and X ⁹ each independently represent at least one selected from the group (AN). Further, X ⁵ , X ⁷ and X ¹⁰ to X ¹² are each independently at least one selected from the group consisting of the following groups (AN-1). X in the group (AN-1) represents N or CR, and R has the same meaning as R described in the CR in the group (AN).

In the general formulae (IV-1) to (IV-8), Y ³ , Y ⁵ to Y ⁷ , and Y ¹² to Y ¹⁵ each independently represent a coordinating atom coordinated by a non-covalent electron pair. A ring, or at least one partial structure selected from the group (UE). Further, Y ² , Y ⁴ , Y ⁸ to Y ¹¹ , and Y ¹⁶ are each independently a ring containing a coordinating atom coordinated by a non-covalent electron pair, or selected from the following group (UE-1) At least one. R in the group (UE-1) is identical to R in the case where the coordinating atom coordinated by the non-covalent electron pair is contained in the partial structure represented by the group (UE).

Group (UE-1) [Chem. 17]

In the general formulae (IV-1) to (IV-8), L ² to L ²⁰ each independently represent a single bond or a divalent linking group. The divalent linking group has the same meaning as the case where L ¹ in the formula (IV) represents a divalent linking group, and the preferred range is also the same.

Further, in order to improve the visible transmittance, the compound (A2-1) preferably does not continuously bond a plurality of π-conjugated groups such as aromatic groups.

The compound (A2-1) is also preferably a compound containing a 5-membered ring or a 6-membered ring.

The compound (A2-1) is also preferably represented by the formula (II) or the formula (III).

(In the formula (II), X ² represents a group containing a coordination site coordinated by an anion. Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ¹ and A ⁵ each independently represent a carbon atom. a nitrogen atom or a phosphorus atom. A ² to A ⁴ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ¹ represents a substituent. R ^X2 represents a substituent. n 2 represents an integer of 0 to 3. .

In the formula (III), X ³ represents a coordination site in which the anion is coordinated. Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁶ and A ⁹ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ² represents a substituent. R ^X3 represents a substituent. N3 represents an integer from 0 to 2)

In the formula (II), X ² represents a group containing a coordination site coordinated by an anion, and for example, may include only the group containing a coordination site coordinated by an anion, which contains an anion The group at which the coordination site is coordinated may also have a substituent. Examples of the substituent which the group having a coordination site coordinated by an anion may have a halogen atom, a carboxyl group, or a heterocyclic group. The heterocyclic group as a substituent may be a monocyclic ring or a polycyclic ring, and may be aromatic or non-aromatic. The number of the hetero atoms constituting the hetero ring is preferably from 1 to 3, more preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom.

In the formula (II), Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, and further preferably a nitrogen atom.

In the formula (II), A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom, and preferably a carbon atom.

In the formula (II), A ² to A ⁴ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ² and A ³ preferably represent a carbon atom. A ⁴ preferably represents a carbon atom or a nitrogen atom.

In the formula (II), R ¹ represents a substituent, and when the atom adjacent to the nitrogen atom of the coordinating atom coordinated by the non-covalent electron pair of the compound (A1) is a carbon atom, The substituents having the carbon atoms have the same meanings, and the preferred ranges are also the same.

In the formula (II), R ^X2 represents a substituent, and the substituent which the ring containing a coordinating atom coordinated by a non-covalent electron pair may have the same meaning, and the preferred range is also the same. R ^{X2 is} preferably any substituent of A ² to A ⁴ in the formula (II), and further preferably, it is not substituted on Y ² .

In the formula (II), n2 represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.

In the formula (III), X ³ represents a group containing a coordination site coordinated by an anion, and has the same meaning as X ² in the formula (II), and the preferred range is also the same.

In the formula (III), Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom.

In the formula (III), A ⁶ and A ⁹ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ^{6 is} preferably a carbon atom or a nitrogen atom. A ^{9 is} preferably a carbon atom.

In the formula (III), A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ^{7 is} preferably a carbon atom. A ⁸ is preferably a carbon atom, a nitrogen atom or a sulfur atom.

In the formula (III), R ² represents a substituent, and has the same meaning as R ¹ in the formula (II), and the preferred range is also the same.

In the formula (III), R ^X3 represents a substituent, and has the same meaning as R ^X2 in the formula (II), and the preferred range is also the same.

In the formula (III), n3 represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.

Further, in order to improve the visible transmittance, R ^X1 and R ^{X2 are} preferably a substituent in which a plurality of π-conjugated groups are not continuously bonded.

The compound (A2-1) is also preferably represented by the following formula (I).

(In the formula (I), X ¹ represents a group containing a coordination site coordinated by an anion. Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring. R ^X1 Represents a substituent, n1 represents an integer from 0 to 6)

In the formula (I), X ¹ represents a group containing a coordination site coordinated by an anion, and has the same meaning as X ² in the formula (II), and the preferred range is also the same.

In the formula (I), Y ¹ represents a nitrogen atom or a phosphorus atom, and together with adjacent carbon atoms constitutes a 4-membered ring to a 7-membered ring. It is particularly preferred that Y ¹ in the formula (I) represents a nitrogen atom and constitutes a 5-membered ring or a 6-membered ring together with an adjacent carbon atom.

In the formula (I), R ^X1 represents a substituent, and the substituent which may be contained in the case where the coordination atom coordinated by the non-covalent electron pair is contained in the ring has the same meaning, and the preferred range is also the same.

Further, in order to improve the visible transmittance, it is preferred that R ^x1 is not a substituent in which a plurality of π-conjugated groups are continuously bonded.

In the formula (I), n1 represents an integer of 0 to 6, preferably 0 to 2, more preferably 0 or 1.

Further, the compound (A2-1) is also preferably represented by the formula (1).

(In the formula (1), R ¹ represents a hydrocarbon group. R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. R ¹ and R ² or R ³ may be bonded to each other to form a ring)

In the formula (1), R ¹ represents a hydrocarbon group, preferably an alkyl group or an aryl group.

In the case where R ¹ in the formula (1) represents an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic chain. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 10, and still more preferably from 1 to 5. Specifically, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. When R ¹ in the formula (1) represents an alkyl group, it may have a more substituent. Examples of the substituent which the alkyl group may have include an alkoxy group, an alkylcarbonyl group, a fluorenyl group, an alkoxycarbonyl group, a halogen atom (for example, a fluorine atom), a heterocyclic group (for example, an oxolane ring, an oxane ring, A dioxolane ring, a furan ring, a dioxane ring, a pyran ring), a polymerizable group (for example, a vinyl group, a (meth)acryl fluorenyl group), or the like. The alkyl group having a substituent may also have a substituent.

In the case where R ¹ in the formula (1) represents an aryl group, the carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12. The aryl group is preferably a phenyl group. In the case where R ¹ in the formula (1) represents an aryl group, it may have a more substituent. The substituent which the alkyl group may have has the same meaning as the case where R ¹ in the formula (1) is an alkyl group.

In the formula (1), R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.

The first aspect of the compound represented by the formula (1) is a form in which both of R ² and R ³ in the formula (1) are a hydrogen atom, and the second aspect is at least R ² and R ³ in the formula (1). A state indicating a halogen atom or a monovalent organic group is preferred.

When R ² and R ³ in the formula (1) represent a halogen atom, a fluorine atom is preferred.

In the case where R ² and R ³ in the formula (1) represent a monovalent organic group, an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 5. Particularly, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 12. The aryl group is preferably a phenyl group.

In the formula (1), it is also preferred that R ¹ and R ² are bonded to each other to form a 5-membered or 6-membered ring containing an oxygen atom, and R ³ is a hydrogen atom.

The 5-membered or 6-membered ring containing an oxygen atom may be an aromatic ring or a non-aromatic ring, preferably a non-aromatic ring. The atom constituting the 5-membered ring or the 6-membered ring containing an oxygen atom is preferably an oxygen atom and a carbon atom. The number of oxygen atoms in the 5-membered ring or the 6-membered ring containing an oxygen atom is preferably from 1 to 3, more preferably 1 or 2, and still more preferably 1. The number of carbon atoms in the 5-membered or 6-membered ring containing an oxygen atom is preferably from 1 to 5, more preferably 4 or 5. Specific examples of the 5-membered or 6-membered ring containing an oxygen atom include an oxolane ring, an oxane ring, a dioxolane ring, a furan ring, a dioxane ring, and a pyran ring.

The compound represented by the formula (1) is also preferably represented by the formula (2).

Formula (2)

(In the formula (2), R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. L represents an n-valent hydrocarbon group or an n-valent group containing a combination of a hydrocarbon group and -O-. n represents an integer from 2 to 6)

In the formula (2), R ¹² and R ¹³ have the same meanings as R ² and R ³ in the formula (1), and preferably all represent a hydrogen atom.

In the formula (2), L represents an n-valent hydrocarbon group or an n-valent group including a combination of a hydrocarbon group and -O-. The hydrocarbon group may be any of a linear chain, a branched chain or a cyclic chain. When the hydrocarbon group is linear, the carbon number is preferably from 2 to 12, more preferably from 2 to 5. The carbon number in the case where the hydrocarbon group is branched is preferably from 3 to 12, more preferably from 6 to 10. The carbon number in the case where the hydrocarbon group is cyclic is preferably from 3 to 12, more preferably from 6 to 12, and still more preferably 6. When the hydrocarbon group is cyclic, it may be an aromatic ring or a non-aromatic ring, preferably a non-aromatic ring.

In the formula (2), n represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3, and still more preferably 2.

The compound represented by the formula (1) preferably has a carboxyl group equivalent of from 1 to 3, more preferably from 1 to 2.

Specific examples of the compound (A2-1) include the following compounds and salts of the following compounds (for example, metal salts (alkali metal salts) such as sodium), but are not limited thereto. Further, the following specific examples are considered to be included in the compound (A1) as well.

[化23]

[Chem. 24]

<<Compound (A2-2)>>

The compound (A2-2) may have two or more coordination atoms coordinated by a non-covalent electron pair in one molecule, and may have three or more, preferably two to four, more preferably Jia has 2 or 3. The compound (A2-2) may be used alone or in combination of two or more.

The compound (A2-2) may have a coordination site coordinated by an anion in the molecule or may have no coordination site coordinated by an anion. Here, the coordination site coordinated by an anion means a coordination site containing an anion which can be coordinated to a copper atom in the copper component, and examples thereof include an oxyanion or a nitrogen anion. The coordination site of the sulfur anion.

In the compound (A2-2), the number of atoms linking the coordinating atoms coordinated by the non-covalent electron pair is preferably from 1 to 6, more preferably from 1 to 3. By setting such a configuration, the structure of the copper complex is more easily deformed, so that the color value can be further increased.

The atoms to which the coordinating atoms coordinated by the non-covalent electron pair are linked to each other may be one type or two or more types. The atom to which the coordinating atoms coordinated by the non-covalent electron pair are bonded to each other is preferably a carbon atom.

In the following exemplified compounds, the coordinating atom coordinated by the non-covalent electron pair is a nitrogen atom, and the atom to which the coordinating atoms coordinated by the non-covalent electron pair are bonded to each other is a carbon atom, and the carbon atom is bonded to the nitrogen atom. The number of atoms is 2.

The number of unsaturated bonds which the compound (A2-2) may have is preferably 9 or less, more preferably 1 to 9.

The molecular weight of the compound (A2-2) is preferably from 50 to 1,000, more preferably from 50 to 600.

In the compound (A2-2), the coordinating atom coordinated by the non-covalent electron pair has the same meaning as the one described in the compound (A1), and the preferred range is also the same.

The compound (A2-2) is also preferably represented by the following formula (V).

Y ¹ -L ¹ -Y ² Formula (V)

(In the general formula (V), Y ¹ and Y ² each independently represent a ring containing a coordinating atom coordinated by a non-covalent electron pair or a partial structure represented by a group (UE). L ¹ represents a single Key or divalent linkage)

In the formula (V), Y ¹ and Y ² are bonded to the ring containing a coordinating atom coordinated by a non-covalent electron pair, or the coordinating atom containing a coordinating pair with a non-covalent electron pair Some of the structures have the same meaning, and the preferred ranges are also the same.

In the general formula (V), when L ¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -SO-, -O-, -SO ₂ - or a group containing a combination of such groups, more preferably an alkylene group having a carbon number of 1 to 3, a phenyl group or a -SO ₂ - group.

A more detailed example of the compound (A2-2) may also be a compound represented by the following formula (V-1) or formula (V-2).

Y ³ -L ² -Y ⁴ -L ³ -Y ⁵ (V-1)

Y ⁶ -L ⁶ -Y ⁷ -L ⁷ -Y ⁸ -L ⁸ -Y ⁹ (V-2)

In the general formulae (V-1) and (V-2), Y ³ , Y ⁵ , Y ⁶ and Y ⁹ each independently represent a ring containing a coordinating atom coordinated by a non-covalent electron pair, or Part of the structure represented by the group (UE).

Further, Y ⁴ , Y ⁷ and Y ⁸ are each independently a ring containing a coordinating atom coordinated by a non-covalent electron pair, or a group selected from the compound (A2-1) (UE-1) At least one of them.

In the general formula (V-1) and the general formula (V-2), L ² to L ⁸ each independently represent a single bond or a divalent linking group. The divalent linking group has the same meaning as the case where L ¹ in the formula (V) represents a divalent linking group, and the preferred range is also the same.

The compound (A2-2) is also preferably a compound having a 5-membered ring or a 6-membered ring.

Specific examples of the compound (A2-2) include the following compounds, but are not limited thereto. Further, the following specific examples are considered to be included in the compound (A1) as well.

<<Compound (A2-3)>>

The monoanionic coordination site in the compound having two monoanionic coordination sites indicates a site which is coordinated to a copper atom via one functional group having a negative charge when coordinated to a copper atom. Examples of the structure having such a monoanionic coordination site include an acid group (phosphoric acid diester group, phosphonic acid monoester group, phosphinic acid group, etc.) containing a phosphorus atom, a sulfo group, a carboxyl group, a hydroxyl group and the like.

The structure having a monoanionic coordination site can form a copper complex by, for example, coordinating with a copper atom as shown below. For example, a carboxyl-copper complex, a phosphodiester-copper complex, a phosphonate mono-copper complex, a phosphinic acid-copper complex, a sulfo-copper complex, a hydroxyl group are formed. Copper complex. Further, the structure having a monoanionic coordination site may be at least one selected from the group (AN).

The compound (A2-3) is a compound represented by the following formula (10).

X ¹ -L ¹ -X ² Formula (10)

(In the formula (10), X ¹ and X ² each independently represent the monoanionic coordination site, and L ¹ represents an alkylene group, an alkenyl group, an extended aryl group, a heterocyclic group, -O-, - S-, -NR ^N1 -, -CO-, -CS-, -SO ₂ -, or a divalent linking group comprising a combination of these groups. Here, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or Aralkyl

In the above formula (10), L ¹ represents an alkylene group, an alkenyl group, an extended aryl group, a heterocyclic group, -O-, -S-, -NR ^N1 -, -CO-, -CS-, - SO ₂ -, or a divalent linking group comprising a combination of such groups. Here, NR ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The alkylene group may, for example, be a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon alkyl group having 3 to 20 carbon atoms, and the like. .

The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. Further, the aryl group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring having a condensation number of 2 to 4. Specific examples thereof include a phenylene group, a naphthyl group, and the like.

The heterocyclic group may be a group having a hetero atom or an aromatic heterocyclic group in the alicyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the heterocyclic group is a monocyclic ring or a condensed ring, 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. Specific examples thereof include a heteroaryl group derived from a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the hetero ring include, for example, an oxolane ring, an oxane ring, a thiolane ring, an oxazole ring, a thiophene ring, a thianthrene ring, a furan ring, a pyran ring, Isobenzofuran ring, chromene ring, xanthene ring, phenoxazine ring, pyrrole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyrazine ring, pyrimidine ring, Pyridazine ring, pyridazine ring, isooxazine ring, anthracene ring, indazole ring, anthracene ring, quinazoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinazoline ring , Cinnoline ring, pteridine ring, indazole ring, carboline ring, phenanthrene, acridine ring, perimidine ring, phenanthroline ring, pyridazine ring , phenarazine ring, phenoxazine ring, furazane ring and the like.

In -NR ^N1 -, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The alkyl group of R ^N1 may be any of a linear chain, a branched chain, and a cyclic chain. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. The cyclic alkyl group may be either a single ring or a polycyclic ring. The cyclic alkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 4 to 14 carbon atoms.

The aryl group of R ^N1 is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and thus preferably unsubstituted. An aryl group having 6 to 14 carbon atoms. Specifically, a phenyl group, a naphthyl group, etc. are illustrated.

The aralkyl group of R ^N1 is preferably a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted aralkyl group having 7 to 15 carbon atoms.

The substituent which the group may have is exemplified by a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group, Carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloxy group, acryloxy group, ether group, sulfonyl group, thioether group, decylamino group, fluorenyl group, hydroxyl group, carboxyl group, aralkyl group , -Si-(OR ^N22 ) ₃ and the like.

Further, the substituent which the group may have may be a group containing at least one of the substituents in combination with at least one of -O-, -CO-, -COO-, and -COOR'. Here, R' is preferably 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.

Examples of the polymerizable group include a polymerizable group containing a carbon-carbon double bond (preferably a vinyl group, a (meth) propylene fluorenyl group), a (meth) acryl fluorenyl group, an epoxy group, or an aziridine group. Wait.

The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. The linear or branched alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 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.

The halogenated alkyl group is preferably an alkyl group substituted with a fluorine atom. In particular, an alkyl group having 2 or more carbon atoms and having 1 to 10 carbon atoms is preferable, and any of a linear chain, a branched chain and a cyclic group may be used, and a linear or branched chain alkane is preferred. base. The alkyl group substituted with a fluorine atom preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group substituted with a fluorine atom preferably has a terminal structure of (-CF ₃ ). The alkyl group substituted with a fluorine atom preferably has a substitution ratio of a fluorine atom of 50% to 100%, more preferably 80% to 100%. Here, the substitution ratio of a fluorine atom means the ratio (%) which substituted the hydrogen atom to a fluorine atom in the alkyl group substituted by a fluorine atom.

In particular, the halogenated alkyl group is more preferably a perfluoroalkyl group, and more preferably a perfluoro group having a carbon number of 1 to 10 alkyl.

In -Si-(OR ^N22 ) ₃ , R ^N22 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3.

Specifically, in the above formula (10), when L ¹ is a group containing a combination of an exoaryl group and -O-, the substituent which the exoaryl group may have is preferably an alkyl group.

In the specific example of the structure represented by L ¹ in the above formula (10), the following structure is preferred.

In the above formula (10), X ¹ and X ² represent the monoanionic coordination site, and more specifically, a carboxyl group, a phosphodiester group, a phosphonic acid monoester group, a phosphinic acid group, a sulfo group, and Hydroxyl and the like.

In the above formula (10), X ¹ and X ² may have the same monoanionic coordination sites as each other, or may have mutually different monoanionic coordination sites.

In the above formula (10), X ¹ and X ^{2 are} preferably a structure represented by the following formula (12), formula (13) or formula (13A).

(In the formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a single bond. Formula (12), general formula (13) and (13A), * indicates a connection portion with the L ¹ )

In the formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.

The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, and thus preferably A substituted or unsubstituted alkyl group having 1 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 substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, more preferably a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms, particularly preferably Substituted cycloalkyl having 4 to 8 carbon atoms.

The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. Specifically, a phenyl group, a naphthyl group, etc. are illustrated.

The aralkyl group is preferably a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably a substituted or unsubstituted aralkyl group having 7 to 16 carbon atoms.

R ¹ in the above formula (12) may have the same substituent as the substituent which L ¹ in the formula (10) may have, and is preferably an alkyl group, an aryl group, an ether group, or Si-(OR ^N22 ) ₃ and the like.

In the above formula (12), A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a single bond. In particular, from the viewpoint of further improving the heat resistance of the composition of the present invention, A ¹ and A ^{2 are} preferably a single bond.

In the specific example of the structure represented by R ¹ in the above formula (12), the following structure is preferred.

<Preparation of copper compound and spectroscopic modifier>

The molar ratio (copper compound: spectroscopic modifier) when the spectroscopic modifier is blended in the copper compound is preferably from 1:0.1 to 1:4.0, more preferably from 1:0.2 to 1-3.

In particular, when the spectroscopic modifier contains a compound having one or more coordinating atoms coordinated by a non-covalent electron pair, the copper atom in the copper compound and the non-covalent electron pair in the spectroscopic modifier are matched. The molar ratio (copper atom: coordinating atom) of the coordination atom of the position is preferably from 1:0.1 to 1:4.0, more preferably from 1:0.3 to 1:2.0, and further preferably from 1:1.0 to 1:2.0. By setting this configuration, the effects of the present invention can be more effectively achieved.

In the step of blending the spectroscopic adjusting agent with the copper compound, the spectroscopic adjusting agent may be blended in the composition containing the copper compound and other components other than the copper compound, or may be set to be substantially different from the spectroscopic adjusting agent in the copper compound. The composition of the solid component. In this case, the solid content other than the copper compound and the spectroscopic modifier is, for example, 1% by mass or less in total.

Further, in the case of spectral adjustment of the copper compound, it is preferred to contain a solvent. The solvent can be exemplified as a solvent which can be blended into an infrared absorbing composition described later. The solvent is preferably formulated in an amount of 10 parts by mass to 900 parts by mass based on 100 parts by mass of the total of the copper compound and the spectroscopic modifier.

The temperature at the time of preparation is preferably from 10 ° C to 40 ° C.

The maximum absorption wavelength of the copper compound after the preparation of the spectroscopic modifier is preferably a maximum absorption wavelength in the range of 700 nm to 1000 nm.

<Near infrared absorbing composition>

The near-infrared absorbing composition of the present invention (hereinafter also referred to as the composition of the present invention) ()) contains a copper compound and a spectroscopic modifier.

According to the composition of the present invention, a near-infrared cut filter which is high in transmittance in the visible range and can achieve high near-infrared shielding properties can be obtained. Further, the film thickness of the near-infrared cut filter can be made thin, which contributes to the reduction in thickness of the camera module.

The copper compound and the spectroscopic adjusting agent have the same meanings as the copper compound and the spectroscopic preparation described in the spectroscopic adjustment method of the near-infrared absorbing material, and the preferred range is also the same.

The content of the copper compound in the composition of the present invention is preferably 1% by mass or more, more preferably 5% by mass, and the upper limit is preferably 60% by mass or less, based on the composition of the present invention (including a solvent). More preferably, it is 40 mass% or less, and further preferably 20 mass% or less.

The content of the spectroscopic modifier in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.25% by mass or more, based on the composition of the present invention (including a solvent). The limit is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less.

The total content of the copper compound and the spectroscopic modifier in the composition of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 8 masses, based on the composition of the present invention (including a solvent). The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The composition of the present invention is preferably contained in an amount of 10% by mass or more, based on the solid content, of copper as an element, more preferably 20% by mass or more, and still more preferably 30% by mass or more. The upper limit does not particularly exist, and is preferably 70% by mass or less, and more preferably 60% by mass or less.

The total solid content of the composition of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, and the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, based on the composition. Good is 35 mass% or less.

The composition of the present invention may contain other components than the copper compound and the spectroscopic modifier as needed. Examples of the other components include a solvent, a curable compound, a polymerization initiator, a binder polymer, a polymerization initiator, and the like. In addition, other near infrared absorbing materials may also be contained.

Solvent

The solvent is not particularly limited as long as the components of the composition of the present invention can be uniformly dissolved or dispersed, and can be appropriately selected according to the purpose. For example, water or an organic solvent can be used.

The solvent is preferably, for example, an alcohol (for example, methanol), a ketone, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, and dimethylformamide, dimethylacetamide, dimethylammonium, or the like.环丁碸 and so on. These solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, a mixed solution of two or more selected from the group consisting of methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate is preferred. Ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol Acid ester, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

Specific examples of the alcohols, the aromatic hydrocarbons, and the halogenated hydrocarbons include the specific examples described in paragraph 0136 of JP-A-2012-194534, and the contents thereof are Enter the specification of this application. Specific examples of the esters, the ketones, and the ethers include the specific examples described in paragraph 0497 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding US Patent Application Publication No. 2012/0235099 [0609]). Further, examples thereof include n-amyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, and ethylene glycol monobutyl ether. Acetate and the like.

The content of the solvent is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more based on the near-infrared absorbing composition. In addition, the upper limit of the content of the solvent is preferably 90% by mass or less, and more preferably 80% by mass or less based on the near-infrared absorbing composition. The solvent may be one type or two or more types. In the case of two or more types, the total amount is in the above range.

Sclerosing compound

The composition of the present invention may also contain a curable compound. The curable compound may be a compound having a polymerizable group (hereinafter sometimes referred to as "polymerizable compound"), or may be 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.

Polymeric compound

The composition of the present invention preferably contains a 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.

The polymerizable compound may be monofunctional or polyfunctional, preferably polyfunctional. By containing a polyfunctional compound, near-infrared shielding properties and heat resistance can be further improved. The number of functional groups is not particularly limited, but is preferably a bifunctional to an octafunctional, more preferably a trifunctional to a hexafunctional.

In the case where the composition of the present invention contains the copper compound and contains a curable compound, preferred examples of the curable compound include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. (preferably a trifunctional to 6-functional (meth) acrylate), a polybasic acid-modified acrylic oligomer, an epoxy resin or a polyfunctional epoxy resin.

Polymerizable monomer and polymerizable oligomer

The first preferred embodiment of the composition of the present invention is a monomer (polymerizable monomer) having a polymerizable group or an oligomer (polymerizable oligomer) having a polymerizable group (hereinafter, polymerizability is sometimes used) The monomer and the polymerizable oligomer are collectively referred to as "polymerizable monomer or the like" as a polymerizable compound.

Examples of the polymerizable monomer and the like can be referred to the description of paragraphs 0033 to 0034 of JP-A-2013-253224, the contents of which are incorporated herein by reference. Among them, the polymerizable compound is preferably an ethoxylated modified pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available) KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercial product is card KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) And the structure of the (meth) acrylonitrile group of these compounds which is separated by an ethylene glycol residue or a propylene glycol residue. In addition, oligomeric forms of these compounds can also be used.

In addition, the description of the polymerizable compound of paragraphs 0034 to 0038 of JP-A-2013-253224 is incorporated herein by reference.

The polymerizable monomer or the like described in the paragraph 0477 of the Japanese Patent Application Laid-Open No. 2012/0235099 (the [0585] of the corresponding US Patent Application Publication No. 2012/0235099) These are incorporated into the specification of the present application. Further, Ethylene Oxide (EO) modified (meth) acrylate (commercially available as M-460; manufactured by Toago Seisakusho Co., Ltd.) is preferred. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred. Oligomer types of these compounds can also be used.

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

The polymerizable monomer or the like may be a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, the ethylene compound may be used as it is in the case of a mixture as described above, and may be used as it is, and if necessary, a non-aromatic carboxylic anhydride may be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used may be exemplified by tetrahydroortylene benzene. Dicarboxylic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Polyfunctional monomer. More preferably, the aliphatic polyhydroxy compound in the ester is pentaerythritol and/or dipentaerythritol. For example, M-305, M-510, M-520, etc. of the Aronix series which are polybasic acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, and more 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 polyfunctional monomer having no acid group is used in combination, the acid value of the entire polyfunctional monomer is adjusted within the above range.

Further, a polyfunctional monolith having a modified structure of caprolactone is preferably used as a polymerizable monomer or the like.

The polyfunctional monolith having a caprolactone-modified structure can be referred to the description of paragraphs 0044 to 0046 of JP-A-2013-253224, the contents of which are incorporated herein by reference.

In the present invention, the polyfunctional monolith having a modified structure of caprolactone may be used alone or in combination of two or more.

Commercial products such as a polymerizable monomer include, for example, a tetrafunctional acrylate SR-494 having four ethylene oxide chains manufactured by Sartomer Co., Ltd., and six manufactured by Nippon Kayaku Co., Ltd. Hexafunctional acrylate with pentyloxy chain DPCA-60, a trifunctional acrylate TPA-330 having three isobutyoxy chains, and the like. In addition, DPCA-20, DPCA-30, DPCA-120, etc. can also be used.

a compound having an epoxy group or an oxetanyl group

A third preferred embodiment of the present invention is a form containing a compound having an epoxy group or an oxetanyl group as a polymerizable compound. The compound having an epoxy group or an oxetanyl group specifically includes 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. Examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic epoxy resin. Further, a monofunctional or polyfunctional glycidyl ether compound is preferred, and a polyfunctional aliphatic glycidyl ether compound is preferred.

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 Denacol EX-212, Denacol EX-214, and Denacol EX-216 which are not low-chlorine products can be similarly used. , Denacol EX-321, generation Deacol EX-850 and so on.

In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN)EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is Edico ( ADEKA) (manufacturing), 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).

A specific example of a polymer having an oxetanyl group in a side chain and a polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule may be used: arronoxaline 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.).

The molecular weight is preferably from 500 to 5,000,000, more preferably from 1,000 to 500,000 by weight.

As the epoxy-unsaturated compound, a glycidyl group such as glycidyl (meth)acrylate or allyl glycidyl ether may be used as the epoxy group, and an unsaturated compound having an alicyclic epoxy group is preferred. Such a compound can be referred to, for example, the description of paragraph 0045 of Japanese Patent Laid-Open Publication No. 2009-265518, and the like. In the application note.

The composition of the present invention may also contain a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group. Specific examples thereof include a polymer (interpolymer) having the following repeating unit. The polymer having the repeating unit described below is preferably a polymer having an epoxy group.

a compound having a partial structure represented by formula (30)

The curable compound used in the present invention may have a partial structure represented by the following formula (30). The curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

[化32]

(In the formula (30), R ¹ represents a hydrogen atom or an organic group)

In the formula (30), 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, a branched or cyclic alkyl group having a carbon number of 3 to 10 (preferably a linear or carbon number having 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 (30), 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 (30). 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 (30) are bonded to each other to form a heterocyclic ring structure (preferably a 5-membered ring structure).

The compound having the partial structure represented by the formula (30) is preferably represented by (the main chain structure of the polymer - the partial structure of the formula (30) - R ¹ ), or by the formula (A- Part of the structure of (30) - B). 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 comprising -(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 and a polymerizable group of the formula (30) group.

In addition, the compound having a partial structure represented by the above formula (30) may have a structure represented by any one of the following formulas (1-1) to (1-5).

(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 represent a hydrogen atom or an organic group of formula (1-5), L ⁴ represents a divalent linking group, R ¹¹ ~ 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 (30), and the preferred range is also the same.

In the formulae (1-3) to (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 any of a linear chain, a branched form, and a cyclic form, 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 (30) may be a monomer or a polymer, preferably a polymer. That is, the compound having the partial structure represented by the formula (30) is preferably a compound represented by the above formula (1-1) or the formula (1-2).

Further, in the case where the compound having the partial structure represented by the formula (30) is a polymer, it is preferred to contain the partial structure in the side chain of the polymer.

Molecular weight of a compound having a partial structure represented by the formula (30) It is preferably 50 to 1,000,000, more preferably 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 the partial structure represented by the above (30) is preferably from 5% by mass to 80% by mass, more preferably from 9% by mass to 60% by mass.

Specific examples of the compound having the partial structure represented by the formula (30) 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 above formula (30) is preferably a polyacrylamide.

Further, specific examples of the compound having a partial structure represented by the formula (30) include a water-soluble polymer, and preferred examples of the main chain structure include polyvinylpyrrolidone and poly(meth)acrylamide. Polyamide, polyvinylpyrrolidone, polyamine Carbamate, polyurea. The water soluble polymer may also be a copolymer, and the interpolymer may also be a random interpolymer.

As the polyvinylpyrrolidone, trade names K-30, K-85, K-90, K-30W, K-85W, and K-90W (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 Indoleamine, N-(phenylsulfonyl) acrylamide, N-(methylsulfonyl) acrylamide, N,N-dimethyl decylamine, N-methyl-N-phenyl propylene Indoleamine, N-hydroxyethyl-N-methylpropenylamine, 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 derivative of the water-soluble polyamine resin, for example, refers to a hydrogen (-CONH-) hydrogen (-atom via methoxymethyl (-CH ₂ OCH ₃ )) using a water-soluble polyamine resin as a raw material. A compound having a structural change in a guanamine bond by substitution or addition reaction of an atom in a water-soluble polyamine resin molecule, like a substituted compound.

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 α- Dimethylamino-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 constituent groups, and thus the hydrogen bonding ability of the polyamide bond of the polyamide resin is greater than that of the N-methoxymethylated nylon.

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 containing the repeating unit having the partial structure represented by the formula (30) 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 3,000. ~1,000,000, more preferably 5,000~200,000.

The amount of the polymerizable compound to be added to the composition of the present invention is preferably 1% by mass or more, more preferably 15% by mass or more, even more preferably 40% by mass or more, and the upper limit value, based on the total solid content of the solvent. It is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.

Further, when a polymer containing a repeating unit having a crosslinking group is used as the polymerizable compound, the content of the polymer is preferably 10% by mass based on the total solid content of the composition of the present invention excluding the solvent. % or more is more preferably 20% by mass or more, and the upper limit is preferably 75% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

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.

<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. When two or more types are used, the total amount is in the following range. The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

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. Benzoin ether compound, ketal derivative compound, thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazo compound, hydrazine compound, hydrazine a compound, an oxazine compound, a benzoin ether compound, a ketal derivative compound, an onium salt compound such as a metallocene compound, an organic boron salt compound, a diterpene compound, a thiol compound, or the like.

The polymerization initiator can be referred to the description of paragraphs 0217 to 0228 of JP-A-2013-253224, the contents of which are incorporated herein by reference.

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). Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name; all manufactured by BASF Japan Co., Ltd.) can be used as a commercial product.

Binder polymer

In order to improve the film properties and the like, the composition of the present invention may further contain a binder polymer in addition to the polymerizable compound. As the binder polymer, an alkali-soluble resin can be preferably used. By containing an alkali-soluble resin, it is effective in the improvement of heat resistance, etc., or the fine adjustment of a coating.

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.

When the binder polymer is contained, the content of the binder polymer is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more based on the total solid content of the composition. The upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less.

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 is preferably 0.0001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass to 0.1% by mass or more based on the solid content of the composition of the present invention. The upper limit is preferably 2% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.1% by mass or less.

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, the composition of the present invention contains a fluorine-based surfactant and an anthrone. At least one of the surfactants is further improved in solution characteristics (particularly fluidity) when it is prepared as a coating liquid. Thereby, the uniformity of the coating thickness or the liquid-saving property is further improved.

In other words, when a film is formed using a coating liquid containing a composition containing at least one of a fluorine-based surfactant and an anthrone-based surfactant, the interfacial tension between the coated surface and the coating liquid is obtained. The wettability of the surface to be coated is improved, and the coatability to the surface to be coated 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 in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the fluorine-based surfactant, and the solubility in the colored photosensitive composition is also good.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraph 0552 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the disclosure of The content is incorporated into the specification of the present application. Commercial products of the fluorine-based surfactant include, for example, Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Meijiafa. (Megafac) F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F479, Meijiafa (Megafac) F482, Megafac F554, Megafac F780, Megafac R08 (above, manufactured by Di Aisheng (DIC) Co., Ltd.).

Examples of the nonionic surfactant include polyoxyethylene ethyl ether, polyoxyethylene ethyl allylate, polyoxyethyl alcohol ester, sorbitan fatty acid ester, and polyoxyethyl ether. Sorbitan fatty acid ester, polyoxyethylene ethylamine, glycerin fatty acid ester, oxygen ethoxylated propyl block copolymer, acetylene glycol surfactant, acetylene polyoxyethylene oxide, etc. . 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, Suffolk (Surfynol) 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol 504, Surfynol CT-111, Sophino (Surfynol) CT-121, Surfynol CT-131, Surfynol CT-136, Surfynol CT-141, Surfynol CT-151, Suffolk (Surfynol) CT-171, Surfynol CT-324, Surfynol DF-37, Surfynol DF-58, Surfynol DF-75, Suffino (Surfynol) DF-110D, Surfynol DF-210, Surfynol GA, Surfynol OP-340, Surfynol PSA-204, Surfino ) PSA-216, Surfynol PSA-336, Surfynol SE, Surfynol SE-F, Surfynol TG, Surfynol GA, Dynol 604 (The above are Nissin Chemicals & Air Products & Chemicals), Olfine A, Olfine B, Olfine AK-02, Orr Olfine CT-151W, Olfine E1004, Olfine E1010, Olfine P, Olfine SPC, Olfine STG, Orr 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, Olfine AF-104, Olfine SK-14, Olfine AE-3 (above is Nisshin Chemical), Acetylenol E00, Acetylenol E13T, Acetylenol E40, Acetylenol E60, Acetylenol E81, Acetylenol E100, Acety Lenol) E200 (all of which are trade names, manufactured by Chuanyan Jinghua Co., Ltd.). Among them, Olfine E1010 is preferred.

In addition, the nonionic surfactant described in JP-A-2012-208494, paragraph 0553 (corresponding to US Patent Application Publication No. 2012/0235099 [0679]), etc. Surfactants, which 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. Also can be exemplified: Toray. "Toray Silicone SF8410", "Toray Silicone SF8427", "Toray Silicone SH8400", "East" manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone ST80PA, Toray Silicone ST83PA, Toray Silicone ST86PA, and TSF-400 manufactured by Momentive Performance Materials ""TSF-401", "TSF-410", "TSF-4446", "KP321", "KP323", "KP324", "KP340" manufactured by Shin-Etsu Chemical Co., Ltd., etc.

Other ingredients

Examples of other components which can be used in combination in the composition of the present invention include 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 use the adhesion promoter on the surface of the substrate and other Auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.).

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

For the above-mentioned components, for example, paragraph number 0183 of the Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. , paragraph number 0103 to paragraph number 0104, paragraph number 0107 to paragraph number 0109, paragraph number 0159 to paragraph number 0184 of Japanese Patent Laid-Open Publication No. 2013-195480, etc., which are incorporated in the specification of the present application. .

<Method for Producing Near Infrared Absorbing Composition>

The method for producing a near-infrared absorbing composition of the present invention comprises the step of formulating a spectroscopic adjusting agent in a copper compound. The step of blending the spectroscopic modifier in the copper compound has the same meaning as that described in the spectroscopic adjustment method of the near-infrared absorbing material.

Further, the method for producing a near-infrared absorbing composition of the present invention may include other steps. For example, a step of blending a copper compound and other components other than the spectroscopic modifier may be further included. Other components other than the copper compound and the spectroscopic modifier described in the near-infrared absorbing composition may be mentioned.

The use of the near-infrared absorbing composition of the present invention is not particularly limited, and examples thereof include a near-infrared cut filter (for example, a near-infrared cut filter for a wafer level lens) on the light receiving side of the solid-state image sensor. solid A near-infrared cut filter or the like on the back side of the body imaging device (opposite to the light receiving side) is preferably a near-infrared cut filter on the light receiving side of the solid-state image sensor. Further, it is preferred that the near-infrared absorbing composition of the present invention is directly applied onto a solid-state image sensor to form a coating film.

The viscosity of the near-infrared absorbing composition of the present invention is preferably 1 mPa when the infrared cut-off layer is formed by coating. 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.

Since the composition of the present invention can be supplied in a coatable state, a near-infrared cut filter can be easily formed on a desired member or position of the solid-state image sensor.

The near-infrared cut filter obtained by using the composition of the present invention preferably has at least one of the following (1) to (9), and more preferably satisfies all of the following (1) to (8). Conditions, and thus all conditions (1) to (9) are satisfied.

(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more.

(2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more.

(3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more.

(4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, further preferably 92% or more, and particularly preferably 95% or more.

(5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(6) The light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(8) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

(9) The light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

Further, the light transmittance of the near-infrared cut filter is preferably 95% or more in the entire range of wavelengths of 450 nm to 500 nm.

The near-infrared cut filter is preferably set to have a film thickness of 300 μm or less, more preferably set to 250 μm or less, further preferably set to 200 μm or less, and more preferably set to 100 μm or less. The lower limit of the film thickness is, for example, preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 20 μm or more. According to the composition of the present invention, since the near-infrared shielding property is high, the film thickness of the near-infrared cut filter can be made thin.

The near-infrared cut filter preferably has a film thickness of 300 μm or less and a light transmittance of 85% or more, more preferably 90% or more, over the entire wavelength range of 400 nm to 550 nm. Further, it is preferable that the light transmittance of at least one of the wavelengths in the range of 700 nm to 800 nm is 20% or less, and more preferably the light transmittance in the entire range of the wavelengths of 700 nm to 800 nm is 20% or less. According to the present invention, a high transmittance visible light range can be ensured Widely, a near-infrared cut filter having high near-infrared shielding properties can be provided.

A near-infrared cut-off filter can be used to have absorption. A lens that cuts off the function of near-infrared rays (a digital camera, a camera lens such as a mobile phone or a car camera, an optical lens such as an f-θ lens or a pickup-up lens), and an optical filter for a semiconductor light-receiving element. A near-infrared absorption filter or a near-infrared absorbing plate for energy-saving blocking heat rays, an agricultural coating agent for the purpose of selectively utilizing sunlight, a recording medium using heat absorption by near-infrared rays, an electronic device or a photographic film Near-infrared filters, safety goggles, sunglasses, hot-line blocking film, optical text reading and recording, confidential document anti-photocopying, electronic photoreceptor, laser welding, etc. In addition, it can also be used as a noise cutoff filter for CCD cameras and a filter for CMOS image sensors.

The present invention also relates to a method for manufacturing a near-infrared cut filter, comprising: applying a near-infrared absorbing composition of the present invention to a light-receiving side of a solid-state image sensor, preferably by dropping, coating or printing; This step of forming a film; and the step of drying. The film thickness, the laminate structure, and the like can be appropriately selected depending on the purpose.

The support to which the composition of the present invention is applied may be a transparent substrate including glass or the like, or may be a solid-state image sensor, or may be another substrate provided on the light-receiving side of the solid-state image sensor, or may be received by a solid-state image sensor. A layer of a flattening layer on the side.

Regarding the method of forming the near-infrared cut filter, for example, by using a dropping method (drop cast), a spin coater, a slit spin coater, a slit coater, screen printing, and applicator coating Wait until implementation. In the case of a dropping method (drop casting), it is preferably A dripping region of a near-infrared absorbing composition having a photoresist as a partition wall is formed on the glass substrate in such a manner that a uniform film is obtained in a predetermined film thickness. Further, the film thickness can be adjusted by the amount of the composition to be dropped, the solid content concentration, and the area of the dropping region.

Further, the drying conditions of the coating film vary depending on the components, the type of the solvent, the ratio of use, and the like, and are usually dried at a temperature of from 60 ° C to 150 ° C for about 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 150 ° C. The heating time in the pre-heating step and the post-heating step is usually from 30 seconds to 240 seconds, preferably from 60 seconds to 180 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.

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 the 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 may 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 160 ° C to 220 ° 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.

The camera module of the present invention includes a solid-state imaging element and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor, and the near-infrared cut filter is a near-infrared cut filter described above.

Further, in the method of manufacturing a camera module of the present invention, a camera module having a solid-state image sensor and a near-infrared cut filter disposed on a light receiving side of the solid-state image sensor is manufactured, and the method of manufacturing the camera module includes the following steps: The near-infrared absorbing composition of the present invention is applied to the light-receiving side of the solid-state image sensor to form a film.

1 is a schematic cross-sectional view showing a configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.

The camera module 10 includes, for example, a solid-state imaging device 11 , a planarization layer 12 provided on the solid-state imaging device 11 , a near-infrared cut filter 13 , and an upper surface of the near-infrared cut filter, and an imaging lens in the internal space. 14 lens mount 15.

In the camera module 10, the incident light h v from the outside is sequentially transmitted through the imaging lens 14 , the near-infrared cut filter 13 , and the planarization layer 12 , and then reaches the imaging element portion 16 of the solid-state imaging device 11 .

The solid-state imaging device 11 includes, for example, an imaging element portion 16, an interlayer insulating film (not shown), a substrate layer (not shown), and color on the main surface of the substrate as a substrate. The color filter 17, an overcoat layer (not shown), and the microlens 18. The color filter 17 (a red color filter, a green color filter, a blue color filter) or the microlens 18 is disposed so as to correspond to the imaging element unit 16 .

Alternatively, the near-infrared cut filter 13 may be provided on the surface of the planarization layer 12, on the surface of the microlens 18, between the matrix layer and the color filter 17, or the color filter 17 may be used. A near-infrared cut filter 13 is provided between the outer coating and the outer coating. For example, the near-infrared cut filter 13 may be disposed at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. When it is provided in 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 shielding property can be further improved.

The near-infrared cut filter of the present invention is available for a reflow soldering step. By manufacturing the camera module by the reflow step, it is possible to automatically mount the electronic component mounting board or the like which must be soldered, and it is possible to particularly improve productivity without using the reflow step. Further, since the mounting can be performed automatically, it is also possible to achieve cost reduction. In the case of the reflow step, it is exposed to a temperature of about 250 ° C to 270 ° C, so the infrared cut filter preferably has heat resistance that can withstand the reflow step (hereinafter also referred to as "reflow-resistant soldering" Sex").

In the specification of the present application, "having resistance to reflow resistance" means maintaining the characteristics as an infrared cut filter before and after heating at 200 ° C for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 ° C for 10 minutes. Further, it is preferable to maintain the characteristics before and after heating at 250 ° C for 3 minutes. In the case of no reflow resistance, the infrared absorption capability of the infrared cut filter may sometimes be maintained under the conditions described. The function of lowering or as a film becomes insufficient.

Further, the present invention is also directed to a method of manufacturing a camera module including the steps of performing a reflow process. The near-infrared cut filter of the present invention maintains the near-infrared absorption capability even if it has a reflow step, so that it does not damage the small size and light weight. The characteristics of a high-performance camera module.

2 to 4 are schematic cross-sectional views showing an example of a peripheral portion of a near-infrared cut filter in the camera module.

As shown in FIG. 2, the camera module can also have a solid-state imaging element 11, a planarization layer 12, and ultraviolet light in sequence. The infrared light reflecting film 19, the transparent substrate 20, the near infrared ray absorbing layer 21, and the antireflection layer 22.

UV. The infrared light reflecting film 19 has an effect of imparting or improving the function of the near-infrared cut filter. For example, the paragraphs 0033 to 0039 of Japanese Patent Laid-Open Publication No. 2013-68688, the contents of which are incorporated herein by reference.

The transparent substrate 20 transmits light of a wavelength in the visible range. For example, reference is made to paragraph 0026 to paragraph 0032 of JP-A-2013-68688, the contents of which are incorporated herein by reference.

The near-infrared absorbing layer 21 can be formed by coating the near-infrared absorbing composition of the present invention.

The anti-reflection layer 22 has a function of improving the light transmittance by preventing reflection of light incident into the near-infrared cut filter, and efficiently utilizing the incident light. For example, refer to paragraph 0040 of Japanese Patent Laid-Open Publication No. 2013-68688, The contents thereof are incorporated into the specification of the present application.

As shown in FIG. 3, the camera module may also have a solid-state imaging element 11, a near-infrared absorbing layer 21, an anti-reflection layer 22, a planarization layer 12, an anti-reflection layer 22, a transparent substrate 20, and ultraviolet light. Infrared light reflecting film 19.

As shown in FIG. 4, the camera module may also have a solid-state imaging element 11, a near-infrared absorbing layer 21, and an ultraviolet ray in sequence. The infrared light reflecting film 19, the planarizing layer 12, the antireflection layer 22, the transparent substrate 20, and the antireflection layer 22.

[Examples]

The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, 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. In addition, "%" and "parts" are quality standards unless otherwise specified.

<copper compound> Synthesis example of copper compound 1

The following 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 at 50 ° C Reaction for 2 hours. After completion of the reaction, the solvent and the produced water were distilled off by an evaporator, whereby copper compound 1 (8.57 g) was obtained.

Synthesis example of sulfonic acid polymer copper compound 1

5.0 g of polyether oxime (manufactured by BASF Corporation, 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 with 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 the following polymer A-1 was obtained. The sulfonic acid group content in the polymer calculated by neutralization titration was 3.0 (meq/g), and the weight average molecular weight (Mw) was 53,000.

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 the sulfonic acid polymer copper compound 1 was obtained.

Synthesis example of low molecular copper sulfonate compound 1

Methanesulfonic acid (2.478 g) was weighed and dissolved in 45 g of methanol to dissolve. 0.5 equivalent of copper acetate (2.341 g) was added to methanesulfonic acid, and the temperature was raised to 50 ° C and reacted for 2 hours. After the reaction is completed, the produced acetic acid and the solvent are distilled off by an evaporator, thereby A low molecular copper sulfonate compound 1 was obtained.

<Spectifying agent>

6-methylpicolinic acid (manufactured by Tokyo Chemical Industry Co., Ltd., pKa=1.01)

6-methoxypicolinic acid (manufactured by Wako Pure Chemical Industries, Ltd., pKa = 3.75)

Pyridine (manufactured by Wako Pure Chemical Industries, Ltd., pKa=5.25)

Piperidine (manufactured by Wako Pure Chemical Industries, pKa=11.24)

Hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd., pKa=10.85)

Example 1

The near-infrared absorbing composition of Example 1 was prepared by mixing the following compounds.

The total solid content concentration in the solvent (water) composition was 20% by mass.

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

<<Spectral change (ε(λmax))>>

Using a spectrophotometer U-4100 (manufactured by Hitachi High-technologies Co., Ltd.), the maximum absorption wavelength was measured at 830 nm. The molar absorption coefficient of the copper compound before the preparation of the spectral modifier and the molar absorption coefficient of the copper compound after the preparation of the spectral modifier. The difference between the measured Mohr absorbance coefficients (the Mohr absorbance coefficient of the copper compound after the spectroscopic adjustment agent was formulated - the Mohr absorbance coefficient of the copper compound before the spectroscopic modifier was formulated) was evaluated.

A: (the molar absorption coefficient of the copper compound after the preparation of the spectroscopic adjusting agent - the molar absorption coefficient of the copper compound before the preparation of the spectroscopic adjusting agent) is 0.4 L/(mol.cm) or more

B: (the molar absorption coefficient of the copper compound after the preparation of the spectroscopic adjusting agent - the molar absorption coefficient of the copper compound before the preparation of the spectroscopic adjusting agent) is 0.3 L / (mol. cm) or more and less than 0.4 L / (mol. cm) )

C: (the molar absorption coefficient of the copper compound after the preparation of the spectroscopic modifier - the molar absorption coefficient of the copper compound before the preparation of the spectroscopic modifier) is 0.2 L/(mol.cm) or more and less than 0.3 L/(mol.cm) )

D: (the molar absorption coefficient of the copper compound after the preparation of the spectroscopic adjusting agent - the molar absorption coefficient of the copper compound before the preparation of the spectroscopic adjusting agent) is less than 0.2 L / (mol. cm)

<<Making of near infrared cutoff filter>>

A photoresist is applied onto the glass substrate, and patterned by lithography to form a partition wall of the photoresist to form a dropping region of the near-infrared absorbing composition. The near-infrared absorbing composition prepared in the examples and the comparative examples was added dropwise to 3 ml, respectively. The substrate having the coating film was dried by allowing to stand at room temperature for 24 hours, and then the coating film thickness was evaluated to find that the film thickness was 192 μm.

<<Heat resistance evaluation>>

The obtained near-infrared cut filter was allowed to stand at 200 ° C for 5 minutes. Before the heat resistance test and the heat resistance test, the maximum absorbance at a wavelength of 700 nm to 1400 nm of the near-infrared cut filter (Absλmax) 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" is 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 the table 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

In Example 1, the molar ratio of the copper atom in the 6-methylpicolinic acid and/or the copper compound to the coordination atom in the spectroscopic modifier (Cu atom: coordinating atom) was changed as described in Table 1 below. In the same manner as in Example 1, except that the near-infrared absorbing composition of each example was prepared, and a near-infrared cut filter was obtained. Further, in the same manner as in Example 1, except that 6-methylpicolinic acid was not used, the near-infrared absorbing composition of Comparative Example 1 was prepared, and a near-infrared cut filter was obtained.

Example 10

The following compound was mixed and the same procedure as in Example 1 was carried out to prepare a near-infrared absorbing composition of Example 10, and a near-infrared cut filter was obtained.

In Example 10, the coordination of the copper atom in the copper compound 1, 6-methylpicolinic acid, and/or copper compound with the spectroscopic modifier was changed as described in Table 2 below. A near-infrared ray absorbing composition of Examples 11 to 19 was prepared in the same manner as in Example 10 except that the molar ratio of the atoms (Cu atoms: coordinating atoms) was used to obtain a near-infrared ray cut filter.

Further, Comparative Example 2 to Comparative Example 4 were prepared in the same manner as in Example 10 except that the copper compound described in the following Table 3 was used as the copper compound, except that the 6-methylpicolinic acid was not used. The near-infrared absorbing composition obtains a near-infrared cut filter.

As is apparent from the above table, it is known that the near-infrared absorbing composition of the embodiment can attain high near-infrared shielding ability and desired spectral characteristics when it is formed into a cured film. Further, in the near-infrared cut filter of the embodiment, the light transmittance at a wavelength of 550 nm is 80% or more, and the transmittance in the visible light range and the shielding property in the near-infrared range can be improved. Further, it was confirmed that the near-infrared cut filter of the example has a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm, and a light transmittance of 20% or less in a range of a wavelength of 800 nm to 900 nm. Further, it is also known that the near-infrared cut filter of the embodiment can ensure a wide visible light range with high transmittance and excellent spectral characteristics.

On the other hand, it is found that the near-infrared absorbing composition of the comparative example is difficult to have both high near-infrared ray shielding ability and desired spectral characteristics when formed into a cured film as compared with the examples.

In the case of the near-infrared absorbing composition prepared in Example 12, when the copper compound 1 is changed to an equivalent amount of a copper complex (17 kinds) having the following sulfonic acid compound as a ligand, Excellent effects were obtained in the same manner as the near-infrared cut filter of Example 12.

In addition to the addition of 5 parts by mass of the polymerizable compound to the near-infrared absorbing composition prepared in Example 12, a near-infrared cut filter was obtained in the same manner. As the polymerizable compound, the following compounds were used. Kayarad (KAYARAD) D-330, KAYARAD D-320, KAYARAD D-310, KAYARAD DPHA, KAYARAD DPCA-20, card KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above manufactured by Nippon Kayaku Co., Ltd.), M-305, M-510 , M-520, M-460 (made in East Asia), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR-494 (manufactured by Sartomer), Denacol EX-212L (long Nagase Chemtex (manufactured by Nagase Chemtex), JER-157S65 (manufactured by Mitsubishi Chemical Corporation). In these cases, an excellent effect can be obtained similarly to the near-infrared cut filter of the twelfth embodiment.

In the near-infrared absorbing composition prepared in Example 12, 1 part by mass of a surfactant was further added, and a near-infrared cut filter was obtained in the same manner. The surfactant is Megafac F171 (made by Diane (DIC)), Surfynol 61 (made by Rixin Chemical Co., Ltd.) or Toray Silicone SF8410 ( Toray-Dow Corning (manufactured by Toray-Dow Corning). In these cases, an excellent effect can be obtained similarly to the near-infrared cut filter of the twelfth embodiment.

In the near-infrared absorbing composition of Examples 1 to 19, the total content of the copper compound relative to the total solid content of the composition is set to 15% by mass, 20% by mass, 30% by mass or 40% by mass. In the case of %, excellent near-infrared shielding ability can be obtained in the same manner as in the above embodiments.

Further, even the near-infrared absorbing compositions of Examples 1 to 19 In the case where the content of the solvent (water) or methanol is 10% by mass, 20% by mass, 30% by mass or 40% by mass, excellent coating properties can be obtained in the same manner as in the above examples.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧Lens mount

16‧‧‧Photographic Components Division

17‧‧‧Color Filter

18‧‧‧Microlens

Claims (15)

A spectroscopic adjustment method for a near-infrared absorbing material, comprising the step of formulating a spectroscopic adjusting agent in a copper compound. The spectroscopic adjustment method of a near-infrared absorbing material according to claim 1, wherein the spectroscopic adjusting agent contains a compound (A1) having one or more coordinating atoms coordinated by a non-covalent electron pair. Or a compound (A2) having at least two coordination sites. The spectroscopic adjustment method of a near-infrared absorbing material according to claim 1, wherein the spectroscopic adjusting agent has at least one coordination site coordinated by an anion and a non-covalent electron pair a compound (A2-1) having a coordinated coordinating atom, a compound (A2-2) having two or more coordinating atoms coordinated by a non-covalent electron pair, or having two monoanionic coordination sites Compound (A2-3). The spectroscopic adjustment method of the near-infrared absorbing material according to the first or second aspect of the invention, wherein the spectroscopic modifier has a pKa of 0.5 to 32. The spectroscopic adjustment method of a near-infrared absorbing material according to the first or second aspect of the invention, wherein the spectroscopic adjusting agent contains one or more coordinating atoms coordinated by a non-covalent electron pair. a compound, wherein a copper atom in the copper compound and a coordination atom of the coordination atom coordinated by the non-covalent electron pair in the spectroscopic modifier are copper atoms: coordination atom = 1: 0.1-1 :4.0. The near-infrared absorbing material as described in claim 1 or 2 A qualitative spectroscopic adjustment method, wherein the copper compound contains a polymer copper complex. A near-infrared absorbing composition comprising a copper compound and a spectroscopic modifier. The near-infrared absorbing composition according to claim 7, wherein the spectroscopic modifier has a pKa of from 0.5 to 32. The near-infrared absorbing composition according to claim 7 or 8, wherein the spectroscopic adjusting agent contains a compound having one or more coordinating atoms coordinated by a non-covalent electron pair. The copper atom in the copper compound and the molar ratio of the coordination atom coordinated by the non-covalent electron pair in the spectroscopic modifier are copper atoms: coordination atom = 1: 0.1 to 1: 4.0 . The near-infrared absorbing composition according to claim 7 or 8, wherein the copper compound contains a polymer copper complex. The near-infrared absorbing composition according to Item 7 or Item 8 of the patent application further contains a curable compound and a solvent. A near infrared ray cut filter which is obtained by hardening a near-infrared absorbing composition according to any one of items 7 to 11. A method for producing a near-infrared ray-cut filter, comprising: a near-infrared absorbing composition according to any one of items 7 to 11 of the invention, which is formed on a light-receiving side of a solid-state image sensor, thereby forming a film A step of. A camera module having a solid-state imaging element and a near-infrared cut filter disposed on a light receiving side of the solid-state imaging element, and the near-infrared cut filter is made in items 7 to 11 of the patent application scope Any of the near A near-infrared cut filter in which an infrared absorbing composition is hardened. A spectroscopic adjusting agent for a copper compound, which comprises a compound (A1) having one or more coordinating atoms coordinated by a non-covalent electron pair or a compound (A2) having at least two coordination sites.