TW201610117A - Near-infrared ray cut filter, near-infrared absorption composition, photo-sensitive resin composition, cured film, compound, camera module, and method for manufacturing camera module - Google Patents

Abstract

Provided are a near-infrared cutoff filter with which it is possible to obtain camera images of good quality; a near-infrared absorbing composition; a photosensitive resin composition; a cured film; a compound; a camera module; and a method for manufacturing a camera module. This near-infrared cutoff filter contains a near-infrared absorbing substance, and has a film thickness of 300 [mu]m or less, transmittance of 85% of above within a wavelength range of 450-550 nm, and transmittance of 10% or less at a 680 nm wavelength.

Description

Near-infrared cut-off filter, near-infrared absorption composition, sensitization Resin composition, cured film, compound, camera module, and camera module manufacturing method

The present invention relates to a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a method of manufacturing a camera module.

In recent years, in a video camera, a digital still camera, a mobile phone with a camera function, etc., a charge coupled device (Charge-Coupled Device, CCD) which is a solid-state imaging element of a color image has been used. Or a Complementary Metal-Oxide-Semiconductor (CMOS) image sensor. Since the solid-state imaging device uses a silicon photodiode that is sensitive to near-infrared light in the light-receiving portion, it is necessary to perform luminosity correction, and in many cases, a near-infrared cut filter (hereinafter also referred to as IR) is used. Cutoff filter).

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

On the other hand, Patent Document 2 discloses the detection of a protein using a squaraine indole compound.

Further, Patent Document 3 discloses a color filter using a squarylium ruthenium compound.

[Prior Art Literature] [Patent Literature]

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

[Patent Document 2] US Patent Application Publication No. 2012/0276642

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-13945

In recent years, in camera modules and the like, further improvement in image quality is required. Therefore, it is desired to develop a near-infrared cut filter having high visible light transmittance and excellent near-infrared light shielding properties.

Therefore, an object of the present invention is to provide a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a camera module capable of obtaining a camera image or the like having excellent image quality. Manufacturing method.

Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <18>.

<1> A near-infrared cut filter comprising a near-infrared absorbing material having a film thickness of 300 μm or less, a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm, and a light transmittance of 10% at a wavelength of 680 nm. the following.

<2> The near-infrared cut filter according to <1>, wherein the near-infrared absorbing material contains the first near-infrared absorbing material and the second near-infrared absorbing material, and the first near-infrared absorbing material is a copper compound, the second near The infrared absorbing material is a compound having a maximum absorption wavelength in a wavelength of 650 nm to 750 nm.

<3> The near-infrared cut filter according to <1> or <2>, which contains a compound represented by the following formula (1) as a near-infrared absorbing material;

In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms; [Chemical 3]

Formula (2), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, the wavy line represents the general formula (1) The link.

<4> The near-infrared cut filter according to <3>, wherein the group represented by the formula (2) is represented by the following formula (3) or (4);

In the formula (3) and the formula (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, and R ¹² represents a substituent. When m is 2 or more, R ¹² may be bonded to each other to form a ring, and X represents The nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer of 0 to 4, and the wavy line indicates a point of attachment to the formula (1).

<5> The near-infrared cut filter according to <3>, wherein R ¹ in the formula (1) is an alkyl group having one or more halogen atoms or an aryl group having one or more halogen atoms. .

The near-infrared cut filter according to any one of <1> to <5> which contains a copper compound as a near-infrared absorbing material, and the copper compound is selected from a phosphorus-containing copper complex and copper sulfonate. At least one of a complex and a copper carboxylate complex.

The near-infrared cut filter according to <2>, wherein the copper compound is at least one selected from the group consisting of a phosphorus-containing copper complex, a copper sulfonate complex, and a copper carboxylate complex.

The near-infrared cut filter according to any one of <1> to <6> which contains the compound represented by the following general formula (A) as a near-infrared absorbing material;

In the general formula (A), Z ¹ and Z ² are each independently a non-metal atomic group of a nitrogen-containing heterocyclic ring forming a condensable ring of 5 or 6 members, and R ¹ and R ² each independently represent an aliphatic group or an aromatic group, L ¹ represents a methine group contains an odd number of methine chains, a and b are independently 0 or 1, when the portion of the formula is represented by Cy cationic unit, X ¹ represents an anion, C Indicates the number necessary for obtaining charge balance. When the portion represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents the number necessary for obtaining charge balance, and Cy in the formula When the charge of the indicated portion is neutralized in the molecule, X ¹ does not exist.

The near-infrared cut filter according to any one of <1> to <7> wherein the film thickness is 200 μm or less.

The near-infrared cut filter according to any one of <1> to <8>, wherein the light transmittance in the range of wavelengths of 400 nm to 575 nm is 85% or more.

The near-infrared cut filter according to any one of <1> to <9>, wherein a light transmittance in a range of wavelengths of 450 nm to 550 nm is 90% or more.

The near-infrared cut filter according to any one of <1> to <10>, wherein a light transmittance in a wavelength range of 700 nm to 1100 nm is 20% or less.

The near-infrared cut filter according to any one of <1> to <11> wherein the light transmittance in the range of 800 nm to 900 nm is 10% or less.

<13> A near-infrared ray absorbing composition which contains a near-infrared ray absorbing material and has a light transmittance of 85% or more and a light transmittance of 680 nm in a wavelength range of 450 nm to 550 nm when a film having a film thickness of 300 μm or less is formed. It is 10% or less.

<14> The near-infrared ray absorbing composition according to <13>, which comprises a copper complex which is at least one selected from the group consisting of a sulfonic acid and a carboxylic acid, and is selected from the following formula (1) At least one of the compound represented by the compound represented by the following formula (A) and the compound represented by the following formula (A);

In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms;

In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) Joint site; general formula (A) [chemical 8]

In the general formula (A), Z ¹ and Z ² each independently represent a non-metallic atomic group forming a nitrogen-containing heterocyclic ring or a fused ring of 5 to 6, R ¹ and R ² each independently represent an aliphatic group or an aromatic group, L ¹ represents a methine group contains an odd number of methine chains, a and b are independently 0 or 1, when the portion of the formula is represented by Cy cationic unit, X ¹ represents an anion, C Indicates the number necessary for obtaining charge balance. When the portion represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents the number necessary for obtaining charge balance, and Cy in the formula When the charge of the indicated portion is neutralized in the molecule, X ¹ does not exist.

<15> A photosensitive resin composition containing a compound represented by the following formula (1);

In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms;

In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) The link.

<16> A cured film obtained by curing the photosensitive resin composition according to <15>.

<17> a compound represented by the following formula (1);

In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms;

In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) The link.

<18> A camera module having a solid-state imaging device and a near-infrared cut filter according to any one of <1> to <12> disposed on a light receiving side of the solid-state imaging device.

<19> A method of manufacturing a camera film set, which is a method of manufacturing the camera module according to <18>, which is characterized in that the light-receiving side of the solid-state image sensor is coated as described in <13> or <14>. The infrared absorbing composition forms a step of forming a near-infrared cut filter.

According to the present invention, it is possible to provide a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a camera module capable of obtaining a camera image or the like having excellent image quality. method.

Further, by containing the compound represented by the formula (1) and/or the formula (A) The compound to be represented is a near-infrared absorbing material, and a near-infrared cut filter excellent in heat resistance can be provided.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧Lens Holder

16‧‧‧Photographic components

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

Fig. 5 is a graph showing the absorption spectrum (DMSO) of Compound I-17.

FIG. 6 is a spectrum diagram showing light transmittance of a film obtained by using the photosensitive resin composition of Example 1. FIG.

FIG. 7 is a spectrum diagram showing the light transmittance of a film obtained by using the photosensitive resin composition of Comparative Example 1. FIG.

8 is a spectrogram showing the light transmittance of a film obtained by using the photosensitive resin composition of Comparative Example 2.

Hereinafter, the contents of the present invention will be described in detail. Furthermore, in the specification of the present application, "~" is based on the numerical values included before and after the lower limit value and The meaning of the limit is used.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means acrylonitrile group and Methyl methacrylate. In addition, in this specification, "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 present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group means a group which participates in a polymerization reaction.

In the expression of the group (atomic group) of the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group).

In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

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

In the present specification, the solid component means a solid component at 25 °C.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, for example, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (Dongcao). (manufactured by Ltd., 6.0 mm ID × 15.0 cm) was used as a column, and a 10 mmol/L lithium bromide N-methylpyrrolidone (NMP) solution was used as a washing liquid.

<Near infrared absorbing composition>

The near-infrared absorbing composition of the present invention contains a near-infrared absorbing material. The near-infrared absorbing material preferably contains a compound having a maximum absorption wavelength in a wavelength of 650 nm to 750 nm, more preferably a cyanine compound, a pyrrolopyrrole compound or a squaraine indole compound, and further preferably contains a compound selected from the group consisting of the following formula (1) The compound represented by the formula (1) and at least one compound represented by the following formula (A) are particularly preferably a compound represented by the following formula (1).

<<Near infrared absorption material>> <<<Compound represented by formula (1)>>>

In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 One or more aryl groups of a halogen atom or a heterocyclic group having one or more halogen atoms.

[Chemistry 14]

In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) The link.

R ¹ in the formula (1) represents an alkyl group having one or more halogen atoms, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms, and more preferably one or more halogen atoms. The alkyl group of the atom or the aryl group having one or more halogen atoms is particularly preferably an alkyl group having one or more halogen atoms.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The fluorine atom reduces the nucleophilicity of the adjacent anion by using a pulling electron (in other words, increases the stability of the anion). Therefore, for example, when it is a fluorine atom, it is difficult to decompose the compound represented by the formula (1) by anion at the time of heating, and heat resistance is particularly improved. Further, the more the number of fluorine atoms, the lower the nucleophilicity of the anion, so that the heat resistance is further improved.

The number of the halogen atoms contained in R ¹ is one or more, and preferably 50% or more of the hydrogen atoms bonded to the carbon atom of the group (alkyl group, aryl group or heterocyclic group) represented by R ¹ are substituted. It is preferably a halogen atom, more preferably 80% or more, and particularly preferably 100%.

The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 8, and particularly preferably from 1 to 3. The alkyl group may be any of a straight chain, a branch, or a ring, and more preferably a straight chain or Branch.

The carbon number of the aryl group is preferably from 6 to 48, more preferably from 6 to 24, and still more preferably 6.

The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Further, the heterocyclic group is preferably 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. The hetero atom contained in the heterocyclic group may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom. The number of heteroatoms is preferably from 1 to 3, more preferably from 1 to 2.

R ^{1 is} preferably a perfluoroalkyl group or a perfluoroaryl group, and particularly preferably a perfluoroalkyl group. Further, the perfluoroalkyl group means a group in which all hydrogen atoms bonded to carbon atoms constituting an alkyl group are substituted with fluorine atoms. In addition, the perfluoroaryl group means a group in which all hydrogen atoms bonded to a carbon atom constituting an aryl group are substituted with a fluorine atom.

A ¹ and A ² in the formula (1) each independently represent an aryl group, a heterocyclic group or a group represented by the formula (2), and are preferably a group represented by the formula (2).

The carbon number of the aryl group represented by A ¹ and A ² is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. Specific examples thereof include a phenyl group and a naphthyl group. Further, the carbon number of the aryl group when the aryl group has a substituent means a number obtained by removing the carbon number of the substituent.

The heterocyclic group represented by A ¹ and A ² is preferably a 5-membered ring or a 6-membered ring. Further, the heterocyclic group is preferably 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, and thus preferably a single A ring or a condensed ring having a condensation number of 2 or 3. The hetero atom contained in the heterocyclic group may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom, and is preferably a nitrogen atom or a sulfur atom. The number of heteroatoms is preferably from 1 to 3, more preferably from 1 to 2. Specifically, a monocyclic or polycyclic aromatic ring-derived heterocyclic group such as a 5-membered ring or a 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom may be mentioned.

The aryl group and the heterocyclic group may also have a substituent. Examples of the substituent include the following.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably a carbon number of 1) ~30 alkyl, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl); The cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms) may, for example, be a cyclohexyl group, a cyclopentyl group or a polycycloalkyl group, and examples thereof include a bicycloalkyl group (preferably carbon). a substituted or unsubstituted bicycloalkyl group of 5 to 30, for example, a bicyclo[1.2.2]heptan-2-yl, a bicyclo[2.2.2]oct-3-yl group or a tricycloalkyl group a polycyclic structure group. Preferred is a monocyclic cycloalkyl group, a bicycloalkyl group, particularly preferably a monocyclic cycloalkyl group; a linear or branched alkenyl group (linear or branched substituted or unsubstituted) Alkenyl group, preferably alkenyl group having 2 to 30 carbon atoms, for example, vinyl group, allyl group, isoprenyl group, geranyl group, oleyl group); cycloalkenyl group (preferably carbon number 3) Examples of the substituted or unsubstituted cycloalkenyl group of ~30 include 2-cyclopentene-1- 2-cyclohexen-1-yl, polycycloalkenyl, such as bicycloalkenyl (preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms, for example, bicyclo [2.2.1] Hept-2-en-1-yl, bicyclo[2.2.2]oct-2-en-4-yl) or tricycloalkenyl, particularly preferably monocyclic cycloalkenyl); alkynyl (preferably carbon) a number of 2 to 30 substituted or unsubstituted alkynyl groups, for example, Ethynyl, propargyl, trimethylallyl ethynyl); aryl (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl , m-chlorophenyl, o-hexadecanylaminophenyl); heterocyclic (preferably substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, single from 5 to 7 members, single a heterocyclic group which is a ring or a condensed ring, more preferably a heterocyclic group wherein the ring constitutes a hetero atom in which the atom is selected from a carbon atom, a nitrogen atom and a sulfur atom and has at least one of a nitrogen atom, an oxygen atom and a sulfur atom, Further, it is preferably a 5-membered or 6-membered aromatic heterocyclic group having a carbon number of 3 to 30. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2- Benzothiazolyl); cyano; hydroxy; nitro; carboxy; alkoxy (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, Isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy); aryloxy (preferably substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, For example, phenoxy, 2-methylphenoxy, 2,4-di- Pentylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy); decyloxy (preferably carbon number 3-20) a decyloxy group, for example, a trimethyl decyloxy group, a tert-butyldimethyl decyloxy group; a heterocyclic oxy group (preferably a substituted or unsubstituted carbon number of 2 to 30) Heteropoly epoxy The heterocyclic moiety is preferably a heterocyclic moiety as described in the heterocyclic group, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); a group (preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as a methyloxy group, B An alkoxy group, a trimethylacetoxy group, a stearyloxy group, a benzyl methoxy group, a p-methoxyphenylcarbonyloxy group; an amine methyl methoxy group (preferably a carbon number of 1 to 30) Substituted or unsubstituted amine mercaptooxy group, for example, N,N-dimethylamine-methylcarbonyloxy, N,N-diethylamine-methylcarbonyloxy, morpholinylcarbonyloxy , N,N-di-n-octylaminocarbonyloxy, N-n-octylamine, fluorenyloxy); alkoxycarbonyloxy (preferably substituted or not having a carbon number of 2 to 30) Substituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy); aryloxycarbonyloxy ( Preferred is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group. P-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy); amine group (preferably amine group, substituted or unsubstituted carbon number 1 to 30) An alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a heterocyclic amino group having 0 to 30 carbon atoms, for example, an amine group, a methylamino group, a dimethylamino group, Anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino); mercaptoamine (preferably from 1 to 30 carbon atoms) a substituted or unsubstituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, Mercaptoamine, etidylamino, trimethylethenylamine, laurylamine, benzhydrylamine, 3,4,5-tri-n-octyloxyphenylcarbonyl Amino) aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, an aminomethylamino group, N,N-dimethylamino group a carbonylamino group, an N,N-diethylaminocarbonylamino group, a morpholinocarbonylamino group; an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxy group having a carbon number of 2 to 30) Alkylcarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonyl group Aminooxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamine Base, m-octyloxyphenoxycarbonylamino); aminesulfonylamino (preferably substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, for example, an amine Sulfhydrylamino, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonyl Alkylsulfonylamino or arylsulfonylamino (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, carbon number 6 to 30) Substituted or unsubstituted arylsulfonylamino group, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorobenzene a sulfonylamino group, a p-methylphenylsulfonylamino group; a fluorenyl group; an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, For example, methylthio, ethylthio, n-hexadecylthio); arylthio (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p- a chlorophenylthio group, a m-methoxyphenylthio group; a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, preferably a heterocyclic ring; a heterocyclic moiety illustrated in the ring group, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group; an aminesulfonyl group (preferably a carbon number of 0 to 30) Substituted or unsubstituted sulfonamide, for example, N-ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonate Sulfhydryl, N-acetamidosulfonyl, N-benzamidesulfonyl, N-(N'-phenylaminecarbamimidino)sulfonyl); sulfo; alkylsulfin Mercapto or arylsulfinyl (preferably substituted or unsubstituted alkylsulfinyl having from 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinylene having from 6 to 30) , for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl); alkylsulfonyl or arylsulfonyl (preferably carbon 1 to 30 substituted or unsubstituted alkylsulfonyl, 6 to 30 substituted or unsubstituted arylsulfonyl, for example, methylsulfonyl, ethylsulfonyl, phenyl Sulfhydryl, p-methylphenylsulfonyl); fluorenyl (preferably a fluorenyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted carbon number of 7 to 30 or Unsubstituted arylcarbonyl group, for example, ethyl hydrazino, trimethylethyl fluorenyl, 2-chloroethyl fluorenyl, stearyl sulfhydryl, benzhydryl, p-positive An octyloxyphenylcarbonyl group; an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, Nitrophenoxycarbonyl, p-t-butylphenoxycarbonyl); alkoxycarbonyl (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, a methoxy group a carbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, an n-octadecyloxycarbonyl group; an amine carbenyl group (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms, For example, amine methyl sulfhydryl, N-methylamine methyl sulfhydryl, N,N-dimethylamine carbhydryl, N,N-di-n-octylamine carbhydryl, N-(methylsulfonyl) An amine carbyl group; an aryl azo group or a heterocyclic azo group (preferably a substituted or unsubstituted aryl azo group having a carbon number of 6 to 30, a substituted carbon number of 3 to 30 or Unsubstituted heterocyclic azo group (the heterocyclic moiety is preferably a heterocyclic moiety as illustrated in the heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethyl Thio-1,3,4-thiadiazol-2-ylazo); quinone imine (preferably substituted or unsubstituted with 2 to 30 carbon atoms) Substituted quinone imine group, for example, N-succinimide group, N-phthalimido group; phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) For example, a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group; a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group; a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy); a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group a decyl group (preferably a substituted or unsubstituted decyl group having a carbon number of 3 to 30, for example, a trimethyl decyl group, a tert-butyl dimethyl decyl group, a phenyl dimethyl decyl group) .

The substituent which the aryl group and the heterocyclic group may have is preferably a halogen atom, an alkyl group, a hydroxyl group, an amine group or a mercaptoamine group.

The halogen atom is preferably a chlorine atom.

The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 5, most preferably from 1 to 4. The alkyl group is preferably a straight chain or a branch.

The amine group is preferably a group represented by -NR ¹⁰⁰ R ¹⁰¹ . R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, further preferably from 1 to 10, particularly preferably from 1 to 8. The alkyl group is preferably a straight chain, a branch, and more preferably a straight chain.

The mercaptoamine group is preferably a group represented by -NR ¹⁰² -C(=O)-R ¹⁰³ . R ¹⁰² represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. R ¹⁰³ represents an alkyl group. The alkyl group represented by R ¹⁰² and R ¹⁰³ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

When the aryl group and the heterocyclic group have two or more substituents, the plurality of substituents may be the same or different.

Next, the group represented by the general formula (2) represented by A ¹ and A ² will be described.

In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) The link.

Formula (2), R ² represents an alkyl group, an alkenyl group or an aralkyl group, preferably an alkyl group.

The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, further preferably from 1 to 12, and particularly preferably from 2 to 8.

The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, and still more preferably from 2 to 12.

The alkyl group and the alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and are preferably a straight chain or a branched chain.

The carbon number of the aralkyl group is preferably from 7 to 30, more preferably from 7 to 20.

In the formula (2), the nitrogen-containing hetero ring formed of Z ^{1 is} preferably a 5-membered ring or a 6-membered ring. Further, the nitrogen-containing hetero ring is preferably 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, and thus preferably A condensed ring having a condensation number of 2 or 3. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to a nitrogen atom. Further, the nitrogen-containing heterocyclic ring may have a substituent. The substituent may have a substituent which the aryl group or the heterocyclic group may have, and the preferred range is also the same. For example, a halogen atom, an alkyl group, a hydroxyl group, an amine group or a mercaptoamine group is preferred, and a halogen atom or an alkyl group is more preferred. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 12. The alkyl group is preferably a straight chain or a branch.

The group represented by the formula (2) is preferably the following formula (3) or formula (4) The base represented.

In the formula (3) and the formula (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, and R ¹² represents a substituent. When m is 2 or more, R ¹² may be bonded to each other to form a ring, and X represents The nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer of 0 to 4, and the wavy line indicates a point of attachment to the formula (1).

R ¹¹ in the general formula (3) and the general formula (4) has the same meaning as R ² in the general formula (2), and the preferred range is also the same.

R ¹² in the general formula (3) and the general formula (4) represents a substituent. The substituent may have a substituent which the aryl group or the heterocyclic group may have, and the preferred range is also the same. For example, a halogen atom, an alkyl group, a hydroxyl group, an amine group or a mercaptoamine group is preferred, and a halogen atom or an alkyl group is more preferred. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 12. The alkyl group is preferably a straight chain or a branch.

When m is 2 or more, R ¹² may be bonded to each other to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a hetero ring. The ring may be a single ring or a heterocyclic ring. The linking group when the substituents are bonded to each other to form a ring may be selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. The divalent linking group in the group is linked. For example, R ¹² is preferably connected to each other to form a benzene ring.

X in the formula (3) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. The substituent may be a substituent which the aryl group or the heterocyclic group may have. For example, an alkyl group etc. are mentioned. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. The alkyl group is preferably a straight chain or a branched chain, and particularly preferably a straight chain.

m represents an integer of 0 to 4, preferably 0 to 2.

The molecular weight of the compound represented by the formula (1) is preferably from 100 to 2,000, more preferably from 150 to 1,000.

The compound represented by the formula (1) preferably has a maximum absorption wavelength in a wavelength of from 600 nm to 800 nm, more preferably a maximum absorption wavelength in the range of from 600 nm to 750 nm, and preferably has a maximum absorption wavelength in the range of from 650 nm to 750 nm.

Specific examples of the compound represented by the formula (1) include the compounds described below, but are not limited thereto. Further, in the following, R ¹ , A ¹ and A ² correspond to the general formula (1), respectively. Further, the wavy line in the group shown by A ¹ and A ² represents a point of attachment to the formula (1).

[table 3]

[Table 4]

[table 5]

The near infrared absorbing composition of the present invention is preferably relative to near infrared rays The total solid content of the absorbent composition is 5% by mass to 90% by mass of the compound represented by the formula (1). The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less.

In addition, it is preferable to contain 0.01 to 50 parts by mass of the compound represented by the formula (1) with respect to 100 parts by mass of the copper compound to be described later. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

By setting it as such a range, it is possible to obtain a near-infrared cut filter which is excellent in barrier properties in a desired range and can cut off infrared rays. For example, a near-infrared cutoff having a spectral thickness of 300 μm or less and a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm and a light transmittance of 10% or less at a wavelength of 680 nm can be obtained. filter.

<<<Compound represented by the general formula (A)>>>

General formula (A)

In the general formula (A), Z ¹ and Z ² each independently represent a non-metallic atomic group forming a nitrogen-containing heterocyclic ring or a fused ring of 5 to 6, R ¹ and R ² each independently represent an aliphatic group or An aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are each independently 0 or 1.

When the moiety represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c represents the number necessary for obtaining charge balance. When the site represented by Cy in the formula is an anion moiety, X ¹ represents a cation. , c denotes the number necessary for obtaining charge balance, and when the charge of the portion indicated by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

In the general formula (A), Z ¹ and Z ² each independently represent a non-metal atomic group of a nitrogen-containing heterocyclic ring of 5 or 6 members which forms a condensable ring.

The nitrogen-containing heterocycle can be condensed with other heterocyclic, aromatic or aliphatic rings. Aza-containing The ring is preferably a 5-membered ring. Further, a nitrogen-containing heterocyclic ring of five members is condensed with a benzene ring or a naphthalene ring. Specific examples of the nitrogen-containing hetero ring include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazolodibenzofuran ring, a thiazole ring, Benzothiazole ring, naphthylthiazole ring, pseudoanthracene ring, benzofluorene ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrolidine a ring, a pyridazine ring, an imidazoquinoxaline ring, a quinoxaline ring, etc., preferably a quinoline ring, a pseudofluorene ring, a benzofluorene ring, a benzoxazole ring, a benzothiazole ring, Benzimidazole ring, particularly preferably a pseudofluorene ring, a benzothiazole ring, a benzimidazole ring.

The nitrogen-containing heterocyclic group and the ring condensed therewith may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an aliphatic group, an aromatic group, a heterocyclic group, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , - NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -NHSO ₂ R ²⁵ or -SO ₂ NR ²⁶ R ²⁷ . R ¹⁰ to R ²⁷ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Further, when R ¹² of -COOR ¹² is hydrogen (i.e., a carboxyl group), the hydrogen atom may be dissociated (i.e., carbonate group) or may be in the state of a salt. Further, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group), and may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aliphatic group may, for example, be an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. These groups may also have a substituent. The substituent may, for example, be a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group or an amine group, and is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group. The hydrogen atom of the carboxyl group and the sulfo group may be dissociated or may be in the form of a salt.

The alkyl group may be cyclic or chain. The chain alkyl group may also have a branch. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, most preferably from 1 to 8. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a cyclopropyl group, a cyclohexyl group, and a 2-ethylhexyl group. Examples of the substituted alkyl group include 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 2-sulfoethyl, 3-sulfoyl. Propyl, 3-sulfobutyl and 4-sulfobutyl, and the like.

The alkenyl group may be cyclic or chain-like. The chain alkenyl group may also have a substituent. The number of carbon atoms of the alkenyl group is preferably from 2 to 20, more preferably from 2 to 12, most preferably from 2 to 8. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 2-pentenyl group, and a 2-hexenyl group.

The alkynyl group may be cyclic or chain-like. The chain alkynyl group may also have a substituent. The alkynyl group preferably has a carbon number of 2 to 20, more preferably 2 to 12, most preferably 2 to 8. Examples of the alkynyl group include an ethynyl group and a 2-propynyl group.

The alkyl portion of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group is the same as the aryl group described later. Examples of the aralkyl group include a benzyl group and a phenethyl group.

In the present invention, the aromatic group may, for example, be an aryl group. The aryl group may also have a substituent. The substituent may be a substituent which the aliphatic group may have, and the preferred range is also the same.

The carbon number of the aryl group is preferably from 6 to 25, more preferably from 6 to 15, most preferably from 6 to 10. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aryl group having a substituent include a 4-carboxyphenyl group, a 4-ethylguanamine phenyl group, a 3-methylsulfonylamino group phenyl group, a 4-methoxyphenyl group, a 3-carboxyphenyl group, and a 3,5- group. Dicarboxyphenyl, 4-methanesulfonamide phenyl and 4-butylsulfonamide phenyl.

In the present invention, the heterocyclic group may have a substituent. As a substituent, The substituents which the aliphatic group may have are listed, and the preferred range is also the same.

The heterocyclic group heterocyclic ring is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring may be a single ring or a condensed ring. Examples of the heterocyclic ring include a pyridine ring, a piperidine ring, a furan ring group, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an anthracene ring, an imidazole ring, a pyrazole ring, and an anthracene. An azole ring, a phenothiazine ring, a phenoxazine ring, a porphyrin ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiadiazole ring.

In the general formula (A), R ¹ and R ² each independently represent an aliphatic group or an aromatic group. Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group. The aromatic group may, for example, be an aryl group. The alkyl group, the alkenyl group, the alkynyl group, the aralkyl group and the aryl group may be exemplified by the substituents described above, and the preferred ranges are also the same. The alkyl group, the alkenyl group, the alkynyl group, the aralkyl group and the aryl group may have a substituent or may be unsubstituted. The substituent may, for example, be a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group or an amine group, and is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group. The hydrogen atom of the carboxyl group and the sulfo group may be dissociated or may be in the form of a salt.

In the formula (A), L ¹ represents a methine chain containing an odd number of methine groups. L ^{1 is} preferably a methine chain containing 3, 5 or 7 methine groups.

The methine group may also have a substituent. The methine group having a substituent is preferably a central (median) methine group. Specific examples of the substituent are the same as those of the nitrogen-containing heterocyclic ring of Z ¹ and Z ² . In addition, the two substituents of the methine chain may also be bonded to form a 5-membered ring or a 6-membered ring.

In the formula (1), a and b are each independently 0 or 1. Preferably a and b is 0. Further, when both a and b are 0, the general formula (1) is represented as follows.

In the general formula (A), when the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, and c represents the number necessary for obtaining a charge balance. Examples of the anion include halide ions (Cl ^- , Br ^- , I ^- ), p-toluenesulfonate ions, ethyl sulfate ions, PF ₆ ^- , BF ₄ ^- or ClO ₄ ^- , and tris(haloalkyl) groups. a sulfonyl) methide anion (eg, (CF ₃ SO ₂ ) ₃ C ^- ), a bis(haloalkylsulfonyl) quinone imine anion (eg, (CF ₃ SO ₂ ) ₂ N ^- ), tetracyano Borate anion and the like.

In the general formula (A), when a portion of Cy in the formula is an anion portion represented, X ¹ represents a cation, c denotes the number for obtaining the necessary charge balance. Examples of the cation include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ^{2+ ,} etc.), and transition metal ions (Ag ⁺ , Fe). ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2+ ,} etc.), other metal ions (Al ^3+, etc.), ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, Tetrabutylammonium ion, cerium ion, tetramethyl phosphonium ion, diazabicycloundecene fluorene, and the like. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , diazabicycloundecene oxime are preferable.

In the general formula (A), when the electric charge of the moiety represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The compound represented by the formula (A) is also preferably a compound represented by the following (1A) or (1B), more preferably a compound represented by the following (1B).

In the formulae (1A) and (1B), R ^1A , R ^2A , R ^1B and R ^2B each independently represent an alkyl group, an alkenyl group, an alkynyl group, an arylalkyl group or an aryl group, and L ^1A and L ^1B are each independently Represents a methine chain containing an odd number of methine groups, and Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 - or -CR ^X2 R ^X3 -, R ^X1 , R ^X2 and R ^X3 Each independently represents a hydrogen atom or an alkyl group, and V ^1A , V ^2A , V ^1B and V ^2B each independently represent a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, Heteroaryl, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ¹⁹ R ²⁰ , -NHCOOR ²¹ , -SR ²² , -SO ₂ R ²³ , -SO ₂ OR ²⁴ , -NHSO ₂ R ²⁵ or -SO ₂ NR ²⁶ R ²⁷ , V ^1A , V ^2A , V ^1B and V ^2B may also form a condensed ring, and R ¹⁰ to R ²⁷ are independently when R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, R ¹² is -COOR ¹² and -SO ₂ oR ²⁴ hydrogen ²⁴ is a hydrogen atom, a hydrogen atom Dissociable, or the state of the salt, m1 and m2 independently represent 0~4, when the part represented by Cy in the formula is cation away When the unit, X ¹ represents an anion, c denotes the number for obtaining the necessary charge balance, when the portion of the formula is an anion represented by Cy unit, X ¹ represents a cation, c denotes for obtaining the necessary charge balance number, when the charge in the formula represented by Cy site and over time in the molecule, X ¹ is absent.

The group represented by R ^1A , R ^2A , R ^1B and R ^2B has the same meaning as the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described in R ¹ and R ² of the formula (A). The preferred range is also the same. These groups may be unsubstituted and may have a substituent. The substituent may, for example, be a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group or an amine group, and is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group. The hydrogen atom of the carboxyl group and the sulfo group may be dissociated or may be in the form of a salt.

When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, a linear alkyl group is more preferred.

Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 - or -CR ^X2 R ^X3 -, preferably -NR ^X1 -.

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, but is preferably a straight chain or a branched chain, and particularly preferably a straight chain. The alkyl group is preferably a methyl group or an ethyl group.

L ^1A and L ^{1B have the} same meanings as L ¹ of the formula (A), and the preferred range is also the same.

The range represented by V ^1A , V ^2A , V ^1B and V ^2B and the substituent of the nitrogen-containing heterocyclic ring of Z ¹ and Z ² of the formula (A) have the same meanings, and a preferred range The same is true.

M1 and m2 independently represent 0 to 4, preferably 0 to 2.

Anionic and cationic range X in the general formula (A), X ¹ represents in ^a same meaning as described, the preferred ranges are also the same.

Specific examples of the compound represented by the formula (A) are shown below. Further, in the following table, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Bn represents a benzyl group, Ph represents a phenyl group, PRS represents C ₃ H ₆ SO ^3- , and BUS represents C ₄ H ₉ SO. ^3- .

[Chemistry 20]

[Table 6]

[Table 7]

[Chem. 21]

The compound represented by the formula (A) can be referred to F.M. Hama (F.M. Harmer) "Heterocyclic Compounds Cyanine Dyes and Related Compounds" (John Wiley & Sons, Inc. - New York, London, 1964) and D.M. DMSturmer, "Heterocyclic Compounds-Specialtopics in heterocyclic chemistry" (Chapter 18, Section 14, 482-515, John Wiley & Sons (John) Wiley & Sons) - New York, London, 1977, "Rodd's Chemistry of Carbon Compounds" (2nd ed., Volume IV, Part B, 1977, Chapter 15, 369 to 422 pages, published by Elsevier Science Publishing Company Inc., New York, Japanese Patent Laid-Open No. Hei 6-313939, and Japanese Patent Laid-Open No. Hei 5-88293, etc., are easily synthesized.

<<<Solid Dispersion>>>

The compound represented by the formula (1) and the compound represented by the formula (A) (hereinafter also referred to as a dye compound) have a compound which forms an association as long as it is dissolved in water. It is preferred to add a gelatin or a salt (for example, barium chloride, potassium chloride, sodium chloride or calcium chloride) to the aqueous solution of the dye compound to form an associate. More preferably, it is a method of adding gelatin to an aqueous solution of a pigment compound.

The association of the pigment compound can also be formed as a solid fine particle dispersion of the pigment compound. For the solid dispersion, for example, "Pigment Dispersion Technology - Method of Using Surface Treatment and Dispersant and Evaluation of Dispersibility" issued by Technology Information Association Co., Ltd., "Pigment Encyclopedia Dictionary" issued by Asakura Bookstore Co., Ltd., and Technical Information Association The latest "Pigment Dispersion" Practice Technology. Case Collection issued by the company has been described in detail. In order to form a solid fine particle dispersion, a known dispersing machine can be used. Examples of dispersing machines include ball mills, vibratory ball mills, planetary ball mills, and sand mills. Machine, rubber mill, jet mill and roller mill. The dispersing machine is described in Japanese Patent Laid-Open No. Sho 52-92716 and International Publication No. 88/074794. A medium or horizontal media disperser is preferred.

Dispersion can also be carried out in the presence of a suitable solvent (for example, water, alcohol, cyclohexanone, 2-methoxy-1-methylethyl acetate). It is preferred to use a surfactant. As the surfactant, an anionic surfactant can be preferably used (described in Japanese Patent Laid-Open No. Sho 52-92716 and International Patent No. 88/074794). An anionic polymer, a nonionic surfactant or a cationic surfactant may also be used as needed.

After the dye compound is dissolved in a suitable solvent, a poor solvent is added to obtain a fine powder. In this case, the surfactant can also be used. Alternatively, the pH may be adjusted to dissolve, and then the pH may be changed to precipitate microcrystals of the pigment. The microcrystals are also associations of pigment compounds. When the pigment compound in the associative state is fine particles (or microcrystals), the average particle diameter is 1000 μm or less, preferably 0.001 μm to 100 μm, more preferably 0.005 μm to 50 μm.

In order to increase the dispersibility of the pigmentation, a previously known resin or Surfactant. As a commercial item, a phthalocyanine derivative (commercial product: EFKA-745 (made by EFKA)), Solsperse 5000 (Jerlikon ( Zeneca) Manufactured; organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer, Polyflow No. 75, No. 90, No. Cationic surfactants such as 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.) and W001 (made by Yushang Co., Ltd.); polyoxyethylene lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide Oleoyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Non-ionic interfacial surfactant; anionic surfactant such as W004, W005, W017 (manufactured by Yushang); EFKA-46, EFKA-47, Ivka EFKA)-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above, Morishita Industry ( () manufacturing), Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Disperse-aid 9100 (made by Sannopco), such as Solsperse 3000, Solsperse 5000, Solsperse 9000, Sonour Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000, etc. Sonopas dispersant (made by zeneca); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adi Copro Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pronik Pluronic) F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Eddie Adeka Pluronic L121, Adeka Pluronic P-123 (made by Asahi Kasei Co., Ltd.) and Ionet (IONET) (made by Sanyo Chemical Co., Ltd.).

As the surfactant, a known surfactant can be appropriately selected, and examples thereof include a cationic surfactant, a fluorine surfactant, and a polymer dispersant.

In addition, a graft copolymer having a monomer having a specific acid amide group and a residue of a quaternary ammonium salt in the main chain portion described in Japanese Laid-Open Patent Publication No. Hei 10-254133 has a dye compound. The excellent effect of microdispersion can be preferably used. By using the graft copolymer, the pigment can be finely dispersed while reducing energy or time consumption, and the dispersed pigment does not aggregate or settle even when it passes, and the dispersion stability can be maintained for a long period of time. These resins may be used singly or in combination of two or more. The amount of the resin to be added is preferably from about 1 part by mass to about 150 parts by mass based on 100 parts by mass of the pigment compound.

<<<Copper Compound>>>

The near-infrared absorbing composition of the present invention preferably further contains a copper compound as an infrared absorbing material. The copper compound can be preferably used in a wavelength range of 700 nm to 1000 nm (near infrared range) having a maximum absorption wavelength.

The copper in the copper compound is preferably monovalent or divalent copper, more preferably divalent copper.

The copper content in the copper compound is preferably from 2% by mass to 40% by mass, more preferably from 5% by mass to 40% by mass.

The copper compound 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. More preferably, the copper salt is copper acetate, copper chloride, copper formate, copper hydroxide, 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 hydroxide, copper benzoate, (methyl) Copper acrylate. The copper salt is preferably a monovalent or 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 can be preferably used. More preferably, it is a copper compound obtained by reacting a compound containing at least one of a sulfonic acid group, a carboxylic acid group, a phosphinic acid group, and a phosphoric acid group with a copper component (hereinafter, these compounds may be referred to as copper sulfonate compounds, respectively). Further, a copper carboxylate compound, a copper phosphinate compound, or a copper phosphate compound) is preferably a copper sulfonate compound, a copper carboxylate compound, and a copper phosphate compound, and more preferably a copper sulfonate compound or a copper carboxylate compound.

The copper compound is preferably a compound represented by the following formula (A).

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

In the formula (A), L represents a ligand coordinated to copper, and 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 atoms which can be coordinated to copper, and preferably has a group having an isolated electron pair of N, O, S or the like. The ligand-based molecule is not limited to one type, and may be contained in two or more types, and may be dissociated or non-dissociated. In the case of non-dissociation, X does not exist.

When the copper compound is a copper complex, the ligand is coordinated to the central metal. The form of copper. The copper component can be obtained by mixing, reacting, or the like with a compound to be a ligand or a salt thereof to obtain a copper complex. Therefore, if the near-infrared absorbing composition contains copper and a ligand, it is expected that a copper complex is formed in the composition.

The compound to be a ligand or a salt thereof is preferably exemplified by an organic acid. a compound or a salt thereof or the like. Examples of the organic acid compound or a salt thereof include phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonate, phosphinic acid, substituted phosphinic acid, sulfonic acid, carboxylic acid, carbonyl (ester, ketone), amine, decylamine. A compound such as sulfonamide, urethane, urea, alcohol, or mercaptan. Preferred among these are phosphoric acid, phosphate, phosphonic acid, phosphonate, phosphinic acid, substituted phosphinic acid, sulfonic acid, carboxylic acid, more preferably phosphate, phosphonate, substituted phosphinic acid, sulfonic acid. ,carboxylic acid.

The compound to be a ligand or a salt thereof is preferably represented by the following formula (i).

General formula (i)

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

In the formula (i), R ^{1 is} preferably a hydrocarbon group or an oxygen alkyl group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, a halogen atom (preferably a fluorine atom), and a polymerizable group (for example, a vinyl group, a (meth)acrylylene group, an epoxy group, and an oxetane group. An alkyl group or the like, a sulfonic acid group, a carboxylic acid group, an acid group containing a phosphorus atom, a carboxylate group (for example, -CO ₂ CH ₃ ), a hydroxyl group, an alkoxy group (for example, a methoxy group), an amine group, an amine group An anthracenyl group, an amine carbaryloxy group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group), or the like. When the hydrocarbon group has a substituent, it may further have a substituent. Examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.

When the hydrocarbon group is monovalent, it is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an aryl group. When the hydrocarbon group is divalent, it is preferably an alkyl group, an aryl group, an oxygen 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.

In the formula (i), X ^{1 is} preferably at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom. X ¹ may be one type or two or more types, preferably two or more types, and more preferably a sulfonic acid group and a carboxylic acid group.

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

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

A preferred embodiment of the compound containing an acid group or a salt thereof may, for example, have (1) The compound of at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom is more preferably (2) a form having two or more acid groups, and further preferably (3) having a sulfonic acid group and a carboxylic acid. The form of the base. These forms are more easily deformed than the structure of the copper complex, so that the color value can be further improved, and the ability to absorb near infrared rays, that is, the infrared absorbing ability can be more effectively exhibited. Further, by using a compound having a sulfonic acid group and a carboxylic acid group, the color value can be further increased.

Hereinafter, the copper compound and the compound forming the ligand will be described in detail.

<<<<Phosphorus-containing copper complex>>>>

The phosphorus-containing copper complex is not particularly limited as long as it has a ligand containing a phosphorus compound, and is preferably a copper phosphate complex, a copper phosphate complex, a copper phosphonate complex, or a phosphonic acid. Copper ester complex, copper phosphinate complex, substituted copper phosphinate More preferably, it is a copper phosphate complex, a copper phosphonate complex, or a substituted copper phosphinate complex.

<<<<<Phosphate Copper Complex>>>>>

The copper phosphate complex is a complex of copper as a central metal and a phosphate compound as a ligand. The phosphate compound which forms a ligand is more preferably a compound represented by the following formula (B).

(HO) _n -P(=O)-(OR ² ) _3-n (B)

In the formula (B), R ² represents an organic group, and n represents 1 or 2.

(Wherein, R ² represents alkyl having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms or aralkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbons or -OR ² represents a polyoxyalkyl group having 4 to 100, a (meth) propylene decyloxy group having 4 to 100 carbon atoms, or a (meth) acryl decyl polyoxyalkyl group having 4 to 100 carbon atoms, and n is 1 or 2 )

When n is 1, R ² may be the same or different.

As a specific example of the phosphate compound, for example, paragraphs 0020 to 0025 of Japanese Patent Laid-Open Publication No. 2013-253224 (paragraphs 0020 to 0025 of the corresponding International Publication WO2013/168824 pamphlet), Japanese Patent Laid-Open No. 2001- The description of paragraphs 0041 to 0045 of the 354 945 (the corresponding [0059] of the specification of the US Patent Application Publication No. 2003/0160217) is incorporated herein by reference.

<<<<<phosphonate copper complex>>>>>

The copper phosphonate complex is a complex of copper as the central metal and a phosphonate compound as a ligand. The phosphonate compound forming the ligand is more preferably a compound represented by the following formula (E).

(In the formula (E), R ³ and R ⁴ each independently represent a monovalent organic group)

The compound represented by the formula (E) and a salt thereof function as a ligand coordinated to copper.

R ³ and R ⁴ in the formula (E) each independently represent a monovalent organic group. The specific monovalent organic group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group, an alkenyl group, an aryl group, and a heteroaryl group. Here, the groups may also be via a divalent linking group in the middle (eg, alkyl, cycloalkyl, aryl, heteroaryl, -O-, -S-, -CO-, -COO). -, - OCO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group) and the like) group. Further, the monovalent organic group may have a substituent.

The linear or branched alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.

The cyclic alkyl group may be either monocyclic or polycyclic. 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.

The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. Further, the heteroaryl 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. Specifically, 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 can be used. Examples of the heteroaryl ring in the heteroaryl group include an oxazole ring, a thiophene ring, a thiathrene ring, a furan ring, a pyran ring, an isobenzofuran ring, and a benzopyran 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, quinazine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinazoline ring, porphyrin Cinnoline ring, pteridine ring, indazole ring, carboline ring, phenanthrine ring, acridine ring, perimidine ring, phenanthroline ring Phenanthroline ring), pyridazine ring, phenarsazine ring, phenoxazine ring, furazan ring, and the like.

The substituent which the monovalent organic group may have is exemplified by an alkyl group, a polymerizable group (for example, a vinyl group, a (meth)acrylylene group, an epoxy group, an oxetanyl group, etc.), a halogen atom, or a carboxyl group. And a carboxylate group (for example, -CO ₂ CH ₃ or the like), a hydroxyl group, a decylamino group, a halogenated alkyl group (for example, a fluoroalkyl group, a chloroalkyl group) or the like. Further, examples of the substituent include a substituent which R ¹ in the above formula (i) may have.

The alkylene group, the aryl group or the heteroaryl group as a divalent linking group may be exemplified by removing one hydrogen source from the linear, branched or cyclic alkyl group, aryl group or heteroaryl group. The resulting divalent linking group is derived.

The molecular weight of the copper phosphate complex represented by the formula (E) is preferably from 200 to 1,000, more preferably from 250 to 750, and still more preferably from 300 to 500.

The copper phosphonate complex is preferably one having the structure represented by the following formula (F).

(In the formula (F), R ³ and R ⁴ each independently represent a monovalent organic group. "*" means a site which forms a coordinate bond with copper)

In the formula (F.), The R ³ and R ⁴ in the formula (E) R ³ and R ⁴ are the same meaning, the preferred ranges are also the same.

Specific examples of the phosphonate copper complex are shown below.

[化25]

<<<<<Substituted copper phosphinate complex>>>>

Substituted copper phosphinate complex is copper as the central metal and substituted phosphinate The complex acts as a complex of the ligand. The substituted phosphinic acid compound which forms a ligand is preferably a compound represented by the following formula (G).

(In the formula (G), R ⁵ and R ⁶ each independently represent a monovalent organic group)

The compound represented by the formula (G) and a salt thereof function as a ligand coordinated to copper.

R ⁵ and R ⁶ in the formula (G) each independently represent a monovalent organic group. The specific monovalent organic group is not particularly limited, and examples thereof are the same as those of the monovalent organic group described in R ³ and R ⁴ in the above formula (E), and the preferred ranges are also the same.

The molecular weight of the substituted phosphinic acid compound represented by the formula (G) is preferably from 50 to 750, more preferably from 50 to 500, and still more preferably from 80 to 300.

The substituted copper phosphinate complex used in the present invention preferably contains a structure represented by the following formula (H).

[化27]

(In the formula (H), R ⁵ and R ⁶ each independently represent a monovalent organic group. "*" means a site which forms a coordinate bond with copper)

In formula (H), the R ⁵ and R ⁶ in the formula (G) wherein R ⁵ and R ⁶ are the same meaning, the preferred ranges are also the same.

Specific examples of the substitution of the copper phosphinate complex are shown below.

Phosphorus-containing copper complexes are made by reacting copper with phosphorus as a ligand A compound (for example, a phosphate, a phosphonate, a substituted phosphinic acid, or the like) or a salt thereof is obtained by reacting.

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 or divalent copper, more preferably divalent copper. As the copper salt, copper acetate, copper chloride, copper formate, copper stearate, and more preferably 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 Preferred are copper acetate, copper chloride, copper sulfate, copper benzoate, and copper (meth)acrylate.

The phosphorus-containing compound can be synthesized, for example, by a known method.

For example, a phosphate compound can be obtained by reacting 2-hydroxyethyl methacrylate, phenyl phosphate, and 1,3,5-triisopropylsulfonium chloride in a pyridine solvent.

The salt of the phosphorus-containing compound is preferably a metal salt, and specific examples thereof include a sodium salt, a potassium salt, a magnesium salt, a calcium salt, and a borate.

The reaction ratio when the copper component is reacted with the phosphorus-containing compound or a salt thereof is preferably set to 1:1.5 to 1:4 in terms of a molar ratio.

Further, the reaction conditions when the copper component is reacted with the phosphorus-containing compound or a salt thereof are preferably set to be reacted at 20 ° C to 50 ° C for 0.5 hour or longer.

It is preferred to have phosphorus-containing copper in a wavelength range of 700 nm to 1000 nm. The maximum absorption wavelength of the complex compound is more preferably in the range of 720 nm to 890 nm, and preferably has a maximum absorption wavelength in the range of 730 nm to 880 nm. The maximum absorption wavelength can be measured, for example, using a Cary 5000 UV/Vis-NIR (spectrophotometer, manufactured by Agilent Technologies, Inc.).

Further, the phosphorus-containing copper complex preferably has a gram absorbance of 0.04 or more (g/mL), more preferably 0.06 or more (g/mL), still more preferably 0.08 or more (g/mL).

The gram absorbance can be calculated, for example, using a Cary 5000 UV-Vis-NIR (spectrophotometer, manufactured by Agilent Technologies, Inc.) apparatus.

<<<<Copper sulfonate complex>>>>

The copper sulfonate complex is a complex of copper as a central metal and a sulfonic acid compound as a ligand. The sulfonic acid compound as a ligand is more preferably a compound represented by the following formula (I).

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

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

General formula (I) in particular R ⁷ a monovalent organic group include a hydrocarbon group, and specific examples include linear, branched or cyclic alkyl group, an alkenyl group, an aryl group. The groups may also be via a divalent linking group (for example, a linear or branched alkyl group, a cyclic extended alkyl group (cyclic cycloalkyl group), an extended aryl group, -O-, a group of -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR- (wherein 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 (i), and a preferred range The same is true.

The monovalent organic group may have a substituent, and examples of the substituent include a substituent which the monovalent organic group represented by R ³ and R ⁴ of the formula (E) 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 at least one selected from the group consisting 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 carboxylic acid methyl group, and a sulfonic acid group is preferred. And at least one of the carboxylic acid groups.

The divalent linking group, that is, a linear or branched alkyl group, a cyclic alkyl group, or an extended aryl group, may be exemplified by the linear or branched or cyclic alkyl group or aryl group. A divalent linking group derived by a hydrogen atom.

Examples of the substituent which the monovalent organic group represented by R ³ and R ⁴ of the formula (E) may be a substituent which the organic group which may be represented by the above formula (E).

Examples of the substituent which the R ⁷ is a linear alkyl group or a branched alkyl group include at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. Examples of the substituent which R ⁷ is an aryl group include 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 carboxylic acid methyl group. It is preferably at least one of a sulfonic acid group and a carboxylic acid group.

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

The copper sulfonate complex preferably has a structure represented by the following formula (J).

(In the formula (J), R ⁸ represents a monovalent organic group. "*" Indicates a coordinate bond with a portion formed of copper)

In the formula (J), R ⁸ has the same meaning as R ⁷ in the formula (I), and the preferred range is also the same.

Specific examples of the copper sulfonate complex are shown below.

[化31]

[化32]

[化33]

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

The copper component has the same meaning as the phosphorus-containing copper complex, and the preferred range is also the same.

As the sulfonic acid compound, a commercially available sulfonic acid can be used, and it can also be synthesized by referring to a known method.

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 is preferably from 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.

The reaction conditions when the copper component is reacted with the sulfonic acid compound or a salt thereof are preferably, for example, reacted at 20 ° C to 50 ° C for 0.5 hour or longer.

The maximum absorption wavelength and gram absorbance of the copper sulfonate complex are the same as those of the phosphorus-containing copper complex, and the preferred range is also the same.

<<Other copper compounds>>

In addition to the above, the copper compound used in the present invention may also use a copper compound having a carboxylic acid as a ligand. The carboxylic acid is, for example, preferably a compound represented by the following formula (K).

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

In the formula (K), R ¹ represents a monovalent organic group. The monovalent organic group is not particularly limited, and for example, has the same meaning as the monovalent organic group R ⁷ in the formula (I), and the preferred range thereof is also the same.

As a specific example of the carboxylic acid, for example, the description of paragraph 0029 of the Japanese Patent Laid-Open Publication No. 2013-253224 (paragraph 0029 of the corresponding International Publication WO2013/168824 pamphlet) can be incorporated into the specification of the present application. .

<<<<Polymer type copper compound>>>>

In the present invention, a copper compound of a polymer type obtained by a reaction of a polymer containing an acid group or a salt thereof and a copper component can be used as the copper compound.

The copper compound is, for example, a polymer copper complex containing a polymer containing an acid group ion site and copper ions. The polymer copper complex has an acid group ion site in a side chain of the polymer, and an acid group ion site is bonded to copper (for example, a coordinate bond), and a crosslinked structure is formed between the side chains starting from copper. Heat resistance can be improved by using a polymer copper complex.

As the copper component, a compound containing divalent copper is preferred. 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 a divalent ketone. As the copper salt, copper hydroxide, copper acetate, and copper sulfate are particularly preferred.

The acid group of the polymer containing an acid group or a salt thereof is not particularly limited as long as it is a group reactive with the copper component, and a group which forms a coordinate bond with the copper component is preferable. Specifically, an 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 ruthenium acid group or the like is preferable. The polymer may have only one type of acid group or two or more types.

Examples of the atom or the atomic group of the salt constituting the acid group include a metal atom such as sodium (particularly an alkali metal atom), and an atomic group such as 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 a main chain and a side chain of the polymer, and is preferably contained at least in a side chain.

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

<<<<<First embodiment of a 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 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, -O-, -S-, and -CO. -, -COO-, -OCO-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group comprising a combination of these.

Examples of the divalent hydrocarbon group include a linear, branched or cyclic alkylene 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 3 ~15, and then preferably 3~6. 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 formula (A1-1), M ¹ atom or atomic group constituting a salt with a sulfonic acid group represented by the atom or atomic group constituting the acid salt of the same meaning as the group, preferably a hydrogen atom or an alkali metal atom.

Other constituent sheets other than the constituent unit represented by the formula (A1-1) For the copolymerization component disclosed in [0112] to [0118] of the specification of U.S. Patent Application Publication No. 2011/0124824, the disclosure of which is incorporated herein by reference. The contents are 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).

[化36]

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 formula (A1-1). In particular, Y ^{2 is} preferably -COO-, -CO-, -NH-, a linear or branched alkyl group, or a group or a single bond comprising a combination of these.

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

When the polymer containing the constituent unit represented by the formula (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.

<<<<<Second embodiment of a polymer containing an acid group or a salt thereof>>>>>>

As the polymer type copper compound, 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 an aromatic group-containing polymer) may be used. A polymeric copper compound obtained by reaction 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. Copper obtained by reacting an acid group or a salt thereof and a copper component with a polymer containing the acid group or a salt thereof and a copper component The compounds have the same meaning, and the preferred ranges are also the same.

The carbon number of the aromatic hydrocarbon group is preferably from 6 to 20, more preferably from 6 to 15, more preferably from 6 to 12. Particularly preferred is phenyl, naphthyl or biphenyl. The aromatic hydrocarbon group may be monocyclic or polycyclic, preferably monocyclic.

The carbon number of the aromatic heterocyclic group is preferably from 2 to 30. The aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The aromatic heterocyclic group 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. The hetero atom contained in the aromatic heterocyclic group may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom, and is preferably a nitrogen atom or an oxygen atom.

When the aromatic hydrocarbon group or the aromatic heterocyclic group has a substituent T, the substituent T is exemplified by an alkyl group, a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), and a halogen atom (a fluorine atom). , chlorine atom, bromine atom, iodine atom), carboxylate group, halogenated alkyl group, alkoxy group, methacryloxy group, acryloxy group, ether group, sulfonyl group, thioether group, decylamino group A mercapto group, a hydroxyl group, a carboxyl group, an aralkyl group or the like is preferably an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms).

In particular, the aromatic group-containing polymer is 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. Polyimide-based polymer, polybenzimidazole-based polymer, polyphenyl-based polymer, phenol resin-based polymer, polycarbonate-based polymer, polyamine-based polymer, 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-)

Polymer having (Ph is a phenyl group, the same below)

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, the contents are incorporated into the specification of the present application.

The polyimine-based polymer can be referred to the description of paragraphs 0047 to 0058 of JP-A-2002-367627 and Japanese Patent Laid-Open No. 2004-35891. The main chain structure described in paragraphs 0018 to 0019 of the report is incorporated into the specification of the present application.

A preferred example of the aromatic group-containing polymer preferably contains the following formula (A1-3) The constituent unit shown.

(In the formula (A1-3), Ar ¹ represents an aromatic hydrocarbon group 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 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 aromatic heterocyclic group, and the preferred range is also the same.

Ar ¹ may have a substituent in addition to -Y ¹ -X ¹ in the formula (A1-3). When Ar ¹ has a substituent, the substituent has the same meaning as the substituent T, and the preferred range is also the same.

In the formula (A1-3), Y ^{1 is} preferably a single bond. When 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)-O-, -SO ₂ -, -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), -C(R ^Y1 )(R ^Y2 )- Or a combination of such combinations. R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

Examples of the hydrocarbon group include a linear, branched or cyclic alkylene group and an extended 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 alkylene 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) 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 acid group or a salt thereof, and the preferred range is also the same.

Containing the structure represented by formula (A1-1), formula (A1-2) or formula (A1-3) The weight average molecular weight of the unitary polymer is preferably 1,000 or more, more preferably from 1,000 to 10,000,000, and further preferably from 3,000 to 1,000,000, particularly preferably from 4,000 to 400,000.

As expressed by the formula (A1-1), the formula (A1-2) or the formula (A1-3) Specific examples of the polymer of the constituent unit include the following compounds and salts of the following compounds, but are not limited thereto.

[化38]

<<Auxiliary near infrared absorbing material>>

The near-infrared absorbing composition of the present invention may further contain an auxiliary near-infrared absorbing material different from the near-infrared absorbing material, in addition to the near-infrared absorbing material. When the near-infrared absorbing composition of the present invention further contains an auxiliary near-infrared absorbing material, it is possible to provide a composition excellent in light transmittance over a wavelength range of 450 nm to 550 nm when a film having a film thickness of 300 μm or less is formed. Things. In addition, it is possible to provide a near-infrared cutoff in which the light-shielding property (near-infrared shielding property) in the near-infrared range is high and the light-transmitting property (visible light transmittance) in the visible light range is high. filter.

As the auxiliary near-infrared absorbing material, a metal oxide is preferable. The metal oxide is preferably a metal oxide having a maximum absorption wavelength in a wavelength range of 800 nm to 2000 nm. For example, tungsten ruthenium oxide (CsWO _x ), quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), and zirconium oxide (ZrO ₂ ) may be mentioned. A metal oxide such as spinel (MgAl ₂ O ₄ ) is preferably tungsten oxide.

The tungsten oxide-based compound is an infrared shielding material which has high absorption of infrared rays (especially, light having a wavelength of about 800 nm to 1200 nm) (that is, high light-shielding property (shielding property) for infrared rays) and low absorption of visible light. Therefore, when the near-infrared absorbing composition of the present invention contains a tungsten compound, it is possible to produce near-infrared rays having high light-shielding property (infrared shielding property) in the infrared range and high light transmittance (visible light transmittance) in the visible light range. Cutoff filter.

The tungsten oxide-based compound is more preferably a tungsten oxide-based compound represented by the following general formula (composition formula) (I).

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

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

0.001≦x/y≦1.1

2.2≦z/y≦3.0

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

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

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

Specific examples of the tungsten oxide-based compound represented by the above formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., preferably Cs _0.33 WO ₃ or Rb _0.33. WO ₃ , and thus preferably Cs _0.33 WO ₃ .

The metal oxide is preferably a microparticle. Average of fine particles of metal oxide The particle diameter is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter is in such a range, the metal oxide is less likely to block visible light by light scattering, and the light transmittance in the visible light range can be further improved. In view of avoiding light scattering, the average particle diameter of the metal oxide is preferably as small as possible, but the average particle diameter of the metal oxide is preferably 1 nm or more for reasons such as ease of handling during production.

Metal oxides are available as commercial products. When the metal oxide is for example In the case of a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by a method of heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (refer to Japanese Patent No. 4096205).

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

The near-infrared absorbing composition of the present invention may also contain no auxiliary near-infrared absorbing material, and when it contains the auxiliary near-infrared absorbing material, it assists the near-infrared absorbing material with respect to the total solid content of the near-infrared absorbing composition of the present invention. The content is preferably from 20% by mass to 85% by mass, more preferably from 30% by mass to 80% by mass, even more preferably from 40% by mass to 75% by mass.

Further, the auxiliary near-infrared absorbing material may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<<Cure 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. The curable compound may be any of chemical forms such as monomers, oligomers, prepolymers, and polymers. As a curable compound, for example, a paragraph 0070 to a paragraph 0191 of Japanese Patent Laid-Open Publication No. 2014-41318 (paragraphs 0071 to 0192 of the corresponding International Publication WO2014/017669 pamphlet), Japanese Patent Laid-Open No. 2014-32380 The description of paragraphs 0045 to 0216, etc., is incorporated into the specification of the present application.

The curable compound is preferably a polymerizable compound. For example, it can be cited that it contains ethylene. A compound such as a unsaturated bond or a cyclic ether (epoxy or oxetane). The ethylenically unsaturated bond is preferably a vinyl group, a styryl group, a (meth) acrylonitrile group or an allyl group.

Specific examples of the curable compound include a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate (preferably a trifunctional to hexafunctional (meth) acrylate), and a polybasic acid. A modified acrylic oligomer, an epoxy resin, a polyfunctional epoxy resin, or the like.

The curable 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 the functional groups is not particularly limited, but is preferably a bifunctional to an octyl functional group, and more preferably a trifunctional to hexafunctional functional group.

When the near-infrared ray absorbing composition of the present invention contains a curable compound, the content of the curable compound is preferably from 1% by mass to 80% by mass based on the total solid content after the solvent is removed. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

The curable compound may be used alone or in combination of two or more. When it is two or more types, it is preferable that the total amount is the said range.

<<<Compounds containing ethylenically unsaturated bonds>>>

As an example of the compound containing an ethylenically unsaturated bond, the description of paragraphs 0033 to 0034 of JP-A-2013-253224 is incorporated herein by reference.

As a compound containing an ethylenically unsaturated bond, it is preferred to extend the ethoxylate modification season. Pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Japan) Chemicals Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available) The product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercial product is KAYARAD DPHA, Nippon Chemical Co., Ltd.) The company manufactures; A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and the structure of the (meth)acryloyl group-separated ethylene glycol residue and propylene glycol residue. In addition, these oligomer types can also be used.

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

In addition, a polymerizable monomer or the like described in paragraph 0477 of the corresponding Japanese Patent Application Laid-Open No. 2012/0235099, the entire contents of which are incorporated herein by reference. In the case description.

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. These types of oligomers can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

The compound containing an ethylenically unsaturated bond may be a polyfunctional monomer, and may also It has an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. When the compound containing an ethylenically unsaturated bond has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is, and if necessary, a non-aromatic carboxylic anhydride can be introduced into the hydroxyl group of the ethylenic compound to be introduced. Acid base. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

A compound containing an ethylenic unsaturated bond having an acid group is aliphatic The ester of a hydroxy compound and an unsaturated carboxylic acid is preferably a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, particularly preferably an ester thereof, fat. The polyhydric compound 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.

A preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, particularly preferably from 5 mg-KOH/g to 30 mg-KOH/g. When 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, it is prepared in such a manner that the acid value of the entire polyfunctional monomer is within the above range.

<<<Compounds with epoxy or oxetanyl group>>>

Specific examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in a side chain and a polymerizable group having two or more epoxy groups in the molecule. Examples of the monomer or oligomer 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.

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

These compounds can be used as a commercial product, and can also be obtained by introducing an epoxy group to a side chain of a polymer.

As a commercial item, for example, Japanese Patent Laid-Open No. 2012-155288 can be referred to. The contents of the paragraphs 0191 and the like are incorporated in the specification of the present application.

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

In addition, 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), JER1031S, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above manufactured by Daicel Chemical Industry), Cyclomer P ACA 200M, Cyclomer P ACA 230AA, Cyclomer P ACA Z250, Cyclomer P ACA Z251, Cyclomer P ACA Z300, Cyclomer P ACA Z320 (The above is manufactured by Daicel Chemical Industry Co., Ltd.).

Further, as a commercial product of the phenol novolac type epoxy resin, JER-157S65, JER-152, JER-154, and JER-157S70 (the above is manufactured by Mitsubishi Chemical Corporation) may be mentioned.

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

As the compound having an epoxy group, a compound having a glycidyl group as an epoxy group such as glycidyl (meth)acrylate or allyl glycidyl ether can be used, and it is preferred that the compound has an alicyclic epoxy group. Saturated compound. Such a compound can be referred to, for example, the description of paragraph 0045 of JP-A-2009-265518, and the like.

The epoxy group-containing or oxetanyl group-containing compound may also contain an epoxy group. A polymer having a sulfobutyl group as a repeating unit. Specifically, a polymer (copolymer) having the following repeating unit can be cited.

<<<Other hardening compounds>>>

Further, as the curable compound, a polyfunctional monomeric body having a modified structure of caprolactone is preferably contained.

As a polyfunctional single body having a modified structure of caprolactone, the description of paragraphs 0044 to 0045 of JP-A-2013-253224 is incorporated herein by reference.

Such a polyfunctional monolith having a modified structure of caprolactone is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (Japanese Patent Laid-Open) In the formulas (1) to (3) of paragraphs 0083 to 0085 of JP-A-2014-041318, m = 1, the number of groups represented by the formula (2) = 2, and the compound in which all R ¹ are hydrogen atoms), DPCA-30 (wherein m=1 in the formula (1) to the formula (3), the number of the groups represented by the formula (2) is 3, and the compound in which all R ¹ are a hydrogen atom), DPCA-60 (described above) In the formulae (1) to (3), m = 1, the number of groups represented by the formula (2) = 6, and all compounds in which R ¹ is a hydrogen atom), DPCA-120 (the formula (1) (3) m = 2, the number of the groups represented by the formula (2) = 6, the compound in which all of R ¹ are a hydrogen atom), and the like.

The polyfunctional monothomer having a caprolactone modified structure may be used alone or in combination of two or more.

Commercially available products include, for example, a tetrafunctional acrylate SR-494 having four ethoxylated chains manufactured by Sartomer Co., Ltd., which has six pentyloxy chains manufactured by Nippon Kayaku Co., Ltd. The hexafunctional acrylate DPCA-60, the trifunctional acrylate TPA-330 having three isobutyoxy chains, and the like.

The curable compound may also have a partial knot represented by the following formula (30) Structure. The curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

(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 same and a divalent linking group. The basis of the combination.

Specific examples of such an organic group are preferably -OR', -SR', or a cyclic group 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 alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms (preferably a linear alkyl group having 1 to 7 carbon atoms). a branched or cyclic alkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms. base.

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, a -OR'(R' is a linear alkyl group having 1 to 5 carbon atoms), and -(CH _{2 )} a group in which _m - (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 form a heterocyclic structure (preferably) The base of the 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 (30) - R ¹ ), or by (A-the (30) Part of the structure - B). Here, A is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. Further, B is a group containing -(CH ₂ ) _m - (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), and a combination of the partial structure of the above (30) and a polymerizable group.

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, and -O-, -CO-, -COO- and A combination of at least one of -NH- is more preferably -(CH ₂ ) _m - (m is an integer of from 1 to 8).

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

Alkyl groups can also be substituted. Further, the alkyl group may be in the form of a chain, a branch or a ring, and is preferably a linear or cyclic alkyl 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, 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. .

In addition, the compound having the partial structure represented by the formula (30) may The monomer may also be 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, when 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 this molecule The amount can be more effectively achieved by the effects of the present invention.

As a compound having a partial structure represented by the formula (30) Examples of the compound include a compound having the following structure or the following exemplified compounds, but are not limited thereto. In the present invention, a compound which is particularly preferably a partial structure represented by the formula (30) is a polypropylene decylamine.

In addition, as a combination of the partial structure represented by the formula (30) Specific examples of the material include a water-soluble polymer. Preferred examples of the main chain structure include polyvinylpyrrolidone, poly(meth)acrylamide, polyamine, and polyvinylpyrrolidone. Polyurethane, polyurea. The water-soluble polymer may also be a copolymer, and the copolymer may also be a random copolymer. The water soluble polymer is preferably a water soluble polyamide resin.

Polyvinylpyrrolidone can be used under the trade names K-30, K-85, K-90, K-30W, K-85W, K-90W (manufactured by Nippon Shokubai Co., Ltd.).

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, and N-benzyl. Acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-tolyl acrylamide, N-(hydroxyphenyl) acrylamide, N-(amine sulfonylphenyl) ) acrylamide, N-(phenylsulfonyl) acrylamide, N-(methylsulfonyl) acrylamide, N,N-dimethyl decylamine, N-methyl-N-benzene Acrylamide, N-hydroxyethyl-N-methylpropenamide, and the like. Further, methacrylamide corresponding to these compounds can also be used in the same manner.

The water-soluble polyamine resin may 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 atom of a guanamine bond (-CONH-) via a water-soluble polyamine resin as a raw material, and a methoxymethyl group (-CH ₂ OCH ₃ ) A compound obtained by changing the structure of 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 refers to a compound having a tertiary amine component in a side chain or a main chain, and examples thereof include an aminoethyl piperazine and a diaminopropyl group. Piperazine, α-dimethylamino-ε-caprolactam and the like.

On the other hand, in the compound obtained by copolymerizing a polyamine resin with a hydrophilic compound, for example, a copolymerization of a polyamine-containing resin has a hydrophilic nitrogen-containing cyclic compound and a polyalkylene group. At least one of the groups consisting of alcohols, the hydrogen bond ability of the guanamine 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) is a reaction product of ε-caprolactam with a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid, and 2) ε- The reaction product of caprolactam 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 Precision Technology 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.

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

<<Polymerization initiator>>

The near-infrared absorbing composition of the present invention may further contain a polymerization initiator. The content of the polymerization initiator is preferably from 0.01% by mass to 30% by mass, more preferably 0.1% by mass. 20% by mass, particularly preferably 0.1% by mass to 15% by mass. The polymerization initiator may be one type or two or more types. When two or more types are used, the total amount is preferably in the above range.

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 purpose.

When light is used to initiate polymerization of the polymerizable compound, a photopolymerization initiator is preferred. The photopolymerization initiator is preferably one which is photosensitive to the ultraviolet range to visible light.

Further, when heat is used to initiate polymerization of the polymerizable compound, a thermal polymerization initiator is preferred. The thermal polymerization initiator is preferably decomposed at 150 ° C to 250 ° C.

As the polymerization initiator, a compound having at least an aromatic group is preferred. For example, a mercaptophosphine compound, an acetophenone type compound, an α-amino ketone compound, a benzophenone type compound, a benzoin ether type compound, a ketal derivative compound, a thioxanthone compound, an anthraquinone compound, and a six An arylbiimidazole compound, a trihalogenated methyl compound, an azo compound, an organic peroxide, a diazonium compound, an anthraquinone compound, an anthraquinone compound, a pyridazine compound, a metallocene compound or the like, an organic salt compound , diterpenoid compounds, thiol compounds, and the like.

As a polymerization initiator, the description of paragraphs 0218 to 0251 of the Japanese Patent Laid-Open Publication No. 2014-41318 (paragraph 0220 to paragraph 0253 of the corresponding International Publication WO2014/017669 pamphlet) can be incorporated into the present disclosure. In the application note.

As a bismuth compound, it can be used as a commercial product. (IRGACURE)-OXE01 (made by BASF), Yi Yijia (IRGACURE)-OXE02 (manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Power Electronic New Material Co., Ltd.), Adeka arc Luz (NADE-831) (made by ADEKA) , Adeka arc Luz NCI-930 (made by Eddy Co.) and so on.

As the acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, all of which are BASF, Japan) can be used as a commercial product. (Manufactured by BASF Japan).

As the mercaptophosphine-based initiator, IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF Corporation, Japan) can be used as a commercial product.

The present invention can also use a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include the compound described in JP-A-2010-262028, the compound 24 described in JP-A-2014-500852, the compound 36 to the compound 40, and the Japanese Patent Laid-Open Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. The content is incorporated into this specification.

<<Alkali soluble resin>>

The near-infrared absorbing composition of the present invention may also contain an alkali-soluble resin. By formulating an alkali-soluble resin, alkali development can be used to form a desired pattern.

The alkali-soluble resin is a linear organic polymer, and may suitably have a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It is selected from at least one alkali-soluble resin which promotes an alkali-soluble group. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable from the viewpoint of developability control. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable. As the alkali-soluble resin, the contents of the following paragraphs 0558 to 5571 of the corresponding Japanese Patent Application Laid-Open No. 2012/0235099 (the [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to. It is incorporated into the specification of this application.

When the near-infrared ray absorbing composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin in the total solid content of the near-infrared ray absorbing composition of the present invention is preferably 1% by mass or more, and may be 2 The mass% or more may be 5% by mass or more, and may be 10% by mass or more. In addition, the content of the alkali-soluble resin in the total solid content of the composition of the present invention may be 80% by mass or less, may be 65% by mass or less, or may be 60% by mass or less, or may be set. It is 15% by mass or less.

Further, when the near-infrared ray absorbing composition of the present invention is used to form a pattern by alkali development, it is of course possible to adopt a form in which no alkali-soluble resin is contained.

<<Interfacial active agent>>

The near-infrared absorbing composition of the present invention may also contain a surfactant. The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.0001% by mass to 2% by mass, more preferably 0.005% by mass to 1.0% by mass, even more preferably 0.01% by mass to 0.1% by mass based on the solid content of the near-infrared absorbing composition of the present invention. %.

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

Particularly, the near-infrared absorbing composition of the present invention contains at least one of a fluorine-based surfactant and an anthrone-based surfactant. Thereby, the solution characteristics (especially fluidity) at the time of preparation of the coating liquid are further improved, and the uniformity of the coating thickness or the liquid-saving property is further improved.

In other words, the near-infrared ray absorbing composition contains at least one of a fluorine-based surfactant and an fluorenone-based surfactant, and the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is wetted. The properties are improved, and the coating property of the coating liquid on the coated surface is improved. Therefore, even when a film of a few micrometers (μm) is formed with a small amount of liquid, a film having a uniform thickness having a small thickness unevenness can be more preferably formed.

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-based surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the near-infrared ray absorbing composition is also good.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of the Japanese Patent Publication No. 2014-41318 (paragraphs 0060 to 0064 of the corresponding International Publication WO2014/17669 pamphlet). This content is incorporated into the specification of the present application.

Examples of commercially available fluorine-based surfactants include Megafac F-171, Megafac F-172, and Megafac. F-173, Megafac F-176, Megafac F-177, Megafac F-141, Megafac F-142, Megafac F-143, Meijia Method (Megafac) F-144, Megafac R30, Megafac F-437, Megafac F-475, Megafac F-479, Megafac F-482 , Megafac F-554, Megafac F-780, Megafac F-781 (above produced by Di Aisheng (DIC)), Fluorad FC430, Fu Fluorad FC431, Fluorad FC171 (above Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC -383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

Further, the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the compound is, for example, 14,000.

As a nonionic surfactant, a polyoxyalkylene alkyl group is exemplified. Ether, polyoxyethylene ethyl alkyl allyl ether, polyoxyethyl alcohol ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene ether A base amine, a glycerin fatty acid ester, an oxygen extended ethyloxy propyl block copolymer, an acetylene glycol type surfactant, an acetylene type polyoxyethylene oxide, or the like. These nonionic surfactants may be used alone or in combination of two or more.

Specific trade names include: surfynol 61, surfynol 82, surfynol 104, surfynol 104E, surfynol 104H, Sophino (surfynol) 104A, surfynol 104BC, surfynol 104DPM, surfynol 104PA, surfynol 104PG-50, surfynol 104S, Sophino (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, Sophino (surfynol) DF-110D, surfynol DF-210, surfynol GA, surfynol OP-340, surfynol PSA-204, surfynol ) PSA-216, Surfynol PSA-336, Surfynol SE, Surfynol SE-F, Surfynol TG, Surfynol GA, Dynol 604 (The above are Nissin Chemicals and 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), Acetylenol E00, Acetylenol E13T, Acetylenol E40, Acetylenol E60, Acetylenol E81, Acetylenol E100 , Acetylenol E200 (all of which are trade names, manufactured by Chuanyan Jinghua Co., Ltd.). Among them, Olfine E1010 is preferred.

In addition, as the non-ionic surfactant, the non-ionic surfactants are specifically described in JP-A-2012-208494, paragraph 0553 (corresponding to US Patent Application Publication No. 2012/0235099, No. [0679]). Ionic surfactants, which are incorporated into the specification of the present application.

As a cationic surfactant, specifically, Japanese Patent Laid-Open The cationic surfactant described in paragraph 0554 of the specification of U.S. Patent Application Publication No. 2012/0235099, the entire contents of which is incorporated herein by reference.

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

As an anthrone-based surfactant, for example, Japanese Patent Laid-Open The anthrone-based surfactants described in paragraph 0556 of the Japanese Patent Application Laid-Open No. 2012/0235099, the entire disclosure of which is incorporated herein by reference. In addition, it can also be illustrated: 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.

<<Solvent>>

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

As the organic solvent, for example, alcohols, ketones, esters, and aromatics are preferably exemplified. Aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethyl hydrazine, cyclobutyl hydrazine, and the like. These 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, ethyl 3-ethoxypropionate, and ethyl is preferred. Cellulolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate , 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 are described in paragraph 0136 of JP-A-2012-194534, and the contents thereof are incorporated in the specification of the present application.

Specific examples of the esters, the ketones, and the ethers are described in paragraph 0497 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding Japanese 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. Acid esters, etc.

As the solvent, at least one selected from the group consisting of cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate, and propylene glycol is preferably used. Methyl ether.

The content of the solvent in the near-infrared absorbing composition of the present invention is preferably from 5% by mass to 90% by mass based on the total solid content of the near-infrared absorbing composition of the present invention, and more preferably from 10% by mass to 80% by mass. The amount of mass%, and thus the best to become 20 The amount of mass % to 75% by mass.

<Polymerization inhibitor>

The near-infrared absorbing composition of the present invention may contain a small amount of a polymerization inhibitor in order to prevent an unnecessary reaction of the curable compound during storage or storage of the composition.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyl The amine sulfonium salt or the like is preferably p-methoxyphenol.

When the near-infrared absorbing composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01% by mass to 5% by mass based on the total solid content of the near-infrared absorbing composition of the present invention.

<<Other ingredients>>

The near-infrared absorbing composition of the present invention may be appropriately selected and used according to the purpose as long as the effects of the present invention are not impaired.

Examples of other components that can be used in combination include a dispersant, a sensitizer, a crosslinking agent (aqueous solution of a crosslinking agent), acetic anhydride, a decane compound, a curing accelerator, a filler, a thermal polymerization inhibitor, a plasticizer, and the like. Further, an adhesion promoter for the surface of the substrate and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, and a surface tension adjustment) may be used in combination. Agent, chain transfer agent, etc.).

For example, refer to paragraphs of Japanese Patent Laid-Open Publication No. 2012-003225 Fall No. 0183~Paragraph No. 0228 (corresponding to US Patent Application Publication No. 2013/0034812 [0237] to [0309]), Japanese Patent Laid-Open No. 2008-250074, Paragraph No. 0101 to Paragraph No. 0102, Japanese Patent JP-A-2008-250074, paragraph number 0103 to paragraph number 0104, paragraph number 0107 to paragraph number 0109 of JP-A-2008-250074, and paragraph number 0159 to paragraph number of JP-A-2013-195480 The contents of 0184 and the like are incorporated into the specification of the present application.

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

<Preparation and use of near-infrared absorbing composition>

Since the near-infrared absorbing composition of the present invention can be formed into a liquid form, for example, the near-infrared ray-absorbing filter can be easily produced by applying the near-infrared absorbing composition of the present invention to a substrate or the like and drying it.

For the purpose of removing foreign matter or reducing defects, it is preferred to filter the infrared absorbing composition by a filter. The filter can be used without particular limitation as long as it has been used for filtration purposes or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamine resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be mentioned ( A filter containing high density, ultra high molecular weight, etc. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably from 0.01 μm to 7.0 μm, more preferably from 0.01 μm to 2.5 μm, even more preferably from 0.01 μm to 1.5 μm. By setting the aperture of the filter to the The range is capable of reliably removing fine foreign matter.

Different filters can also be combined when using filters. At this time, the filtration by the first filter may be performed only once or twice or more. When two or more filters are combined by using different filters, it is preferred that the pore diameter after the second filtration is larger than the pore diameter of the first filtration. Further, it is also possible to combine the first filters having different pore diameters within the above range. The aperture here can be referred to the nominal value of the filter maker. Commercially available filters are available, for example, from Pall Co., Ltd., Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (formerly Japan, Mykrolis) )))) or various filters provided by KITZ Micro Filter Co., Ltd., etc.

The second filter can be formed of the same material or the like as the first filter. The pore diameter of the second filter is preferably from 0.5 μm to 7.0 μm, more preferably from 2.5 μm to 7.0 μm, still more preferably from 4.5 μm to 6.0 μm. By setting the pore diameter of the filter to the above range, the foreign matter which prevents the preparation of the uniform and smooth light-shielding composition in the subsequent step can be removed in the state in which the component particles contained in the composition liquid mixture remain.

For example, after filtering by the first filter, other components may be added to perform the second filtration.

The viscosity of the infrared absorbing composition, for example, when formed into an infrared absorbing layer by coating, is preferably at 1 mPa. s~3000mPa. The scope of s. The lower limit is preferably 10 mPa. Above s, more preferably 100mPa. s above. The upper limit is preferably 2000 mPa. Below s, more preferably 1500mPa. s below.

When the near infrared ray cut filter is formed by coating, the viscosity of the near infrared absorbing composition of the present invention is preferably 1 mPa. s~3000mPa. s, more preferably 10mPa. s~2000mPa. s, and then preferably 100mPa. s~1500mPa. s.

When the near-infrared ray absorbing composition of the present invention is a near-infrared cut filter for a light-receiving side of a solid-state image sensor, and a near-infrared cut filter is formed by coating, thick film formability and uniform coatability are obtained. In terms of opinion, it is preferably 10 mPa. s~3000mPa. s, more preferably 500mPa. s~1500mPa. s, and then preferably 700mPa. s~1400mPa. s.

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

The use of the near-infrared absorbing composition of the present invention is not particularly limited It can be preferably used for the formation of a near-infrared cut filter or the like. For example, it can be preferably used for a near-infrared cut filter (for example, a near-infrared cut filter for a wafer level lens) of a solid-state image sensor, and a back side of a solid-state image sensor (and A near-infrared cut filter or the like on the opposite side of the light receiving side. In particular, it can be preferably used as a near-infrared cut filter on the light receiving side of a solid-state image sensor.

<Near-infrared cut filter>

Next, the near-infrared cut filter of the present invention will be described.

The near-infrared cut filter of the present invention is obtained by hardening the near-infrared absorbing composition of the present invention.

Next, the near-infrared cut filter of the present invention will be described.

The near-infrared cut filter of the present invention contains a near-infrared ray absorbing material and has a film thickness of 300 μm or less, a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm, and a light transmittance of 10% or less at a wavelength of 680 nm. Spectroscopic characteristics.

The near-infrared cut filter of the present invention preferably has a light transmittance satisfying at least one of the following (1) to (10), and particularly preferably satisfies all the conditions.

(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 680 nm is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 5% or less.

(6) 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.

(7) 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.

(8) 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.

(9) 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.

(10) 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.

The film thickness of the near-infrared cut filter of the present invention can be adapted according to the purpose When it is selected, it is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less. In addition, the lower limit of the film thickness of the near-infrared cut filter of the present invention is not particularly limited, and is, for example, preferably 1 μm or more, more preferably 2 μm or more, and still more preferably 4 μm or more.

The near-infrared cut filter of the present invention has a film thickness of 300 μm or less and a light transmittance in a range of wavelengths of 400 nm to 550 nm of 85% or more, more preferably 90% or more.

The near-infrared cut filter of the present invention has a light transmittance of 10% or less at a wavelength of 680 nm, preferably 8% or less.

The near-infrared cut filter of the present invention has a film thickness of 300 μm or less, and preferably has a light transmittance of at least one wavelength in a wavelength range of 700 nm to 1100 nm of 20% or less, and more preferably in a wavelength range of from 700 nm to 1100 nm. The light transmittance is 20% or less.

The near-infrared cut filter of the present invention has a film thickness of 300 μm or less, and preferably has a light transmittance of at least one wavelength of 10% or less in a wavelength range of 800 nm to 900 nm, and more preferably a wavelength range of 800 nm to 900 nm. The light transmittance inside is 10% or less.

According to the present invention, it is possible to ensure a wide range of visible light with high transmittance, and it is possible to provide a near-infrared cut filter having high near-infrared shielding properties.

The near infrared cut filter of the present invention can be used for 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 absorption plate for energy-saving blocking heat rays, an agricultural coating agent for the purpose of selectively utilizing sunlight, a recording medium that absorbs heat by using near-infrared rays, an electronic device or a photo 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 is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Method of Manufacturing Near Infrared Cut Filter>

The near-infrared cut filter of the present invention can be produced by forming a film by applying (preferably dropping, coating or printing) the near-infrared absorbing composition of the present invention to a support; and Dry. The film thickness, the laminate structure, and the like can be appropriately selected depending on the purpose. Further, the step of forming a pattern may be further performed.

The step of forming the film can be carried out, for example, by using a dropping method (drop cast), a spin coater, a slit spin coater, a slit coater, screen printing, applicator coating, or the like. The infrared absorbing composition is applied to a support. In the case of a dropping method (drop casting), it is preferred to form a droplet of a near-infrared absorbing composition having a photoresist as a partition wall on a support having a predetermined film thickness so that a uniform film can be obtained. Plus area. Further, regarding the film thickness, the amount of the composition to be dropped, the solid content concentration, and the area of the dropping region can be adjusted. The thickness of the film after drying is not particularly limited and may be appropriately selected depending on the purpose. The thickness of the film is, for example, preferably from 1 μm to 500 μm, more preferably from 1 μm to 300 μm, particularly preferably from 1 μm to 200 μm. In the present invention, even when such a film is used, the near-infrared ray blocking property can be maintained.

The support may be a transparent substrate including glass or the like. In addition, it may be a solid-state imaging element. Further, it may be another substrate provided on the light receiving side of the solid-state image sensor. Further, it may be a layer such as a planarization layer provided on the light receiving side of the solid-state image sensor.

In the step of drying the film, the drying conditions vary depending on the components, the type of the solvent, the ratio of use, and the like, and are carried out at a temperature of 60 ° C to 150 ° C for about 30 seconds to 15 minutes.

The step of forming a pattern includes, for example, a method of applying the near-infrared absorbing composition of the present invention to a support to form a film-like composition layer; and exposing the composition layer to a pattern; The unexposed portion is developed and removed to form a pattern. As a step of forming a pattern, a pattern can be formed by a photolithography method, or a pattern can be formed by a dry etching method.

In the method of manufacturing the near-infrared cut filter, other steps may be included. The other steps are not particularly limited and may be appropriately selected depending on the purpose. For example, 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 can be exemplified.

<<Preheating step. Post heating step >>

The heating temperature in the pre-heating step and the post-heating step is preferably 80 ° C~ 200 ° C, more preferably 90 ° C ~ 150 ° C. The heating time in the pre-heating step and the post-heating step is preferably from 30 seconds to 240 seconds, more preferably from 60 seconds to 180 seconds.

<<hardening treatment steps>>

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. For example, a full-surface exposure treatment, a full-surface heat treatment, or the like can be preferably exemplified. Here, the "exposure" in the present invention is intended to include not only light of various wavelengths but also irradiation of radiation such as electron beams and 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, for example, 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 entire surface exposure treatment may, for example, be a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, the curing of the polymer component in the film formed by the composition is promoted by the entire surface exposure, and the hardening of the film proceeds further, mechanical strength and durability. Improved.

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

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

The heating temperature for the entire surface 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 it is 250° C. or lower, the components in the film are prevented from being decomposed and the film quality is weak and brittle.

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

The apparatus for heating the entire surface 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.

<Manufacturing method of camera module and camera module>

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 imaging element.

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 film is formed by applying the near-infrared absorbing composition of the present invention to the light-receiving side of the solid-state image sensor.

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

The camera module 10 includes, for example, a solid-state imaging element 11 and a solid-state imaging element. The planarization layer 12 on the principal surface side (light receiving side) of the device, the near-infrared cut filter 13, and the lens holder 15 disposed above the near-infrared cut filter and having the imaging lens 14 in the internal space.

In the camera module 10, the incident light hν 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 of the solid-state imaging device 11.

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

Alternatively, a near-infrared cut filter 13 may be provided instead of the surface of the planarization layer 12, and between the surface of the microlens 18, the substrate layer and the color filter 17, or the color filter 17 and the outer coating. A near-infrared cut filter 13 is provided between the layers. 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 set at this position, the step of forming the near-infrared cut filter can be simplified, and the unnecessary near-infrared rays to the microlens can be sufficiently cut off, so that the near-infrared ray blocking 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. Furthermore, since it can be performed automatically, it can also Achieve cost reduction. When it is supplied to the reflow step, it is exposed to a temperature of about 250 ° C to 270 ° C, so the near infrared cut filter preferably has heat resistance that can withstand the reflow step (hereinafter also referred to as "reflow resistance" ").

In the present specification, "having resistance to reflow resistance" means maintaining the characteristics as a near-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. When the reflow resistance is not obtained, the infrared absorbing ability of the near-infrared cut filter may be lowered or the function as a film may be insufficient when held under the above-described conditions.

Further, the present invention relates to a method of manufacturing a camera module including the step 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 of the camera module.

As shown in FIG. 2, the camera module sequentially has a solid-state imaging element 11, a planarization layer 12, and ultraviolet light. Infrared light reflecting film 19, transparent substrate 20, near-infrared absorbing layer (near-infrared cut filter) 21, and anti-reflection 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, reference is made to 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 a visible range, for example, Japanese patents can be referred to. The contents of the paragraph 0026 to paragraph 0032 of Japanese Laid-Open Patent Publication No. 2013-68688 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 transmittance and preventing efficient use of incident light by preventing reflection of light incident on the near-infrared cut filter, and for example, refer to paragraph 0040 of JP-A-2013-68688 The content is incorporated into the specification of this application.

As shown in FIG. 3, the camera module can also have solid imaging elements in sequence. 11. Near-infrared absorbing layer (near-infrared cut-off filter) 21, anti-reflection layer 22, planarization layer 12, anti-reflection layer 22, 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 (near-infrared cut-off filter) 21, and ultraviolet light. The infrared light reflecting film 19, the planarizing layer 12, the antireflection layer 22, the transparent substrate 20, and the antireflection layer 22.

<compound>

Next, the compounds of the present invention will be described.

The compound of the present invention is a compound represented by the formula (1) described in the near-infrared absorbing material of the near-infrared absorbing composition of the present invention, and the preferred range is also the same as the above range.

Although the reason for the detailed description is not clear, the group represented by R ¹ of the compound of the present invention contains a halogen atom, and heat resistance and light resistance can be improved. Further, the transmittance in the range of 650 nm to 750 nm can be further reduced. In particular, by containing a fluorine atom as a halogen atom, heat resistance can be further improved. When the nucleophilicity of the adjacent anion (in other words, the stability of the anion is increased) is lowered by the pulling action of the fluorine atom, it is considered that it is difficult to decompose the compound represented by the general formula (1) by the anion during heating. Sexual improvement. Further, it is considered that the more the number of fluorine atoms is, the more the nucleophilicity of the anion is lowered, so that the heat resistance is improved.

The compound of the present invention preferably has a maximum absorption wavelength in the range of 600 nm to 800 nm in a chloroform solution, more preferably a maximum absorption wavelength in the range of 600 nm to 750 nm, and preferably has a maximum absorption wavelength in the range of 650 nm to 750 nm.

The compound of the present invention can be preferably used, for example, for forming a near-infrared cut filter or the like that blocks light having a wavelength of 600 nm to 800 nm. In addition, it can also be used as a near-infrared absorption filter for solid-state perturbation elements such as a plasma display panel (PDP) or CCD, an optical filter in a heat-shielding filter, and a write-once optical disc (CD-R). Or flashing the photothermal conversion material in the melt fixing material. In addition, it can also be used as an information display material in security ink or invisible bar code ink.

<Photosensitive resin composition>

Next, the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention is a composition of the compound represented by the formula (1) described in the near-infrared absorbing material containing the near-infrared absorbing composition of the present invention. The compound represented by the formula (1) has the same meaning as the compound represented by the above formula (1), and the preferred range is also the same.

Further, the photosensitive resin composition of the present invention may further contain the near-infrared absorption It is preferable that the other component other than the compound represented by the formula (1) described in the composition of the composition contains the curable compound. The cured film obtained by curing the photosensitive resin composition of the present invention can be used for a near-infrared cut filter or the like.

[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. Hereinafter, DMSO is an abbreviation for dimethyl hydrazine.

(Synthesis Example 1) Synthesis of Compound I-17

Raw material 1 was synthesized according to the method described in the literature ("Helvetica Chimica Acta", Vol. 88, pp. 1135 - 1143, 2005).

0.4 g of raw material 1 and trifluorosulfonamide (Tokyo finished product) of 0.21 g was dissolved in 20 ml of chloroform, and 0.1 g of triethylamine and a catalytic amount of dimethylaminopyridine were added. The mixture was heated under reflux for 3 days, and after cooling, the obtained crude crystals were separated by filtration, and purified by a silica gel column chromatography (washing liquid was chloroform or methanol) to obtain a target. Compound (blue solid) I-17. The yield was 55%.

NMR (400MHz, DMSO-d6): δ 1.30 (t, 6H), 4.22 (d, 4H), 4.90 (s, 2H), 7.18 (d, 2H), 7.30 (t, 2H), 7.38 (d, 2H), 7.85 (d, 2H) The absorption spectrum (DMSO) is shown in Fig. 5. The maximum absorption wavelength is 670 nm.

(Synthesis Example 2) Synthesis of Compound I-21

Compound I-21 was synthesized in the same manner as in Synthesis Example 1.

NMR (400MHz, DMSO-d6): δ 1.30 (t, 6H), 4.50 (d, 4H), 4.95 (s, 2H), 7.40 (d, 2H), 7.52 (d, 2H), 7.70 (s, 2H)

The absorption spectrum (DMSO) has a maximum absorption wavelength of 670 nm.

(Synthesis Example 3) Synthesis of Compound I-22 [Chem. 46]

Compound I-22 was synthesized in the same manner as in Synthesis Example 1.

NMR (400MHz, DMSO-d6): δ 1.23 (t, 6H), 4.30 (d, 4H), 4.70 (s, 2H), 7.20 (d, 2H), 7.58 (t, 2H), 7.90 (d, 2H), 8.05 (d, 2H), 8.20 (d, 2H)

The absorption spectrum (DMSO) has a maximum absorption wavelength of 700 nm.

<Preparation of photosensitive resin composition>

1.98 parts by mass of the alkali-soluble resin shown below, 1.69 parts by mass of the compound shown in Table 6, and 0.19 parts by mass of A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polymerizable compound, as photopolymerization Initiator of IRGACURE OXE 01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzamide)], BASF, Japan ) manufactured by the company, 0.09 parts by mass, 0.01 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 1.0% propylene glycol monomethyl group of Megafac F781 (manufactured by Di Aisheng Co., Ltd.) as a fluorine-based surfactant 0.76 parts by mass of an ether acetate (PGMEA) solution and 4.53 parts by mass of PGMEA as a solvent were mixed and stirred, and a nylon filter having a pore diameter of 0.5 μm was used (Japan The Pall (manufactured by Pall) company was filtered to prepare a photosensitive resin composition.

Alkali-soluble resin: the following structure (Mw: 14000, acid value 30 mgKOH/g)

Comparative Compound 1: The following structure

Comparative Compound 2: The following structure ("Chemical Communication", Vol. 49, p. 4764, compound described in 2013) [Chem. 49]

Each of the photosensitive resin compositions was applied onto a glass substrate by a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film. Further, the thickness of the coating film was adjusted so that the thickness (average thickness) of the film was 0.8 μm. Then, the coating film was subjected to heat treatment for 120 seconds using a hot plate at 100 °C.

Then, light of a wavelength of 365 nm was exposed at 1000 mJ/cm ² using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon).

<heat resistance>

After the obtained film was heated at 200 ° C for 5 minutes, the color difference ΔEab value before and after the heat resistance test was measured by a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). It shows that the ΔEab value is small and the heat resistance is good.

In addition, the ΔEab value is a value obtained from the following color difference formula obtained by the CIE1976 (L*, a*, b*) spatial color system (edited by the Japan Color Society, "New Color Science Handbook (1985)" , page 266).

△Eab={(△L*) ² +(△a*) ² +(△b*) ² } ^1/2

<<Judgement benchmark>>

5: △ Eab value < 3

4:3≦△Eab value<5

3:5≦△Eab value<10

2:10≦△Eab value<20

1:20≦△Eab value

<Light resistance>

The resulting film was irradiated with a Xe lamp through a UV cut filter for 10 hours at 10,000 lux, and then the color difference ΔEab before and after the light resistance test was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). value.

<<Judgement benchmark>>

5: △ Eab value < 3

4:3≦△Eab value<5

3:5≦△Eab value<10

2:10≦△Eab value<20

1:20≦△Eab value

[Table 8]

According to the results, Example 1 to implementation using the compound of the present invention The photosensitive resin composition of Example 3 is excellent in heat resistance and light resistance.

On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 2 which did not contain the compound of the present invention were inferior in heat resistance.

Example 1 was compared using a spin coater (manufactured by Sanken Co., Ltd.) The photosensitive resin compositions of Example 1 and Comparative Example 2 were applied to a glass substrate to form a coating film. Further, the thickness of the coating film was adjusted so that the thickness (average thickness) of the film was 0.8 μm. Then, the coating film was subjected to heat treatment (prebake) for 120 seconds using a hot plate at 100 °C.

Then, light of a wavelength of 365 nm was exposed at 1000 mJ/cm ² using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon).

The exposed film was heated at 130 ° C or 200 ° C for 5 minutes or at 200 ° C for 5 minutes.

The ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-technologies) (reference (ref.) glass substrate) was used to measure the heat treatment of only prebaking, and after prebaking, further to 130 The light transmittance in the range of 400 nm to 1000 nm of the film which was heated for 5 minutes at ° C or 200 ° C.

The results are shown in Figures 6 to 8. 6 is a spectrum diagram showing light transmittance of a film obtained by using the photosensitive resin composition of Example 1, and FIG. 7 is a spectrum showing light transmittance of a film obtained by using the photosensitive resin composition of Comparative Example 1. FIG. 8 is a spectrum diagram showing light transmittance of a film obtained by using the photosensitive resin composition of Comparative Example 3. FIG. In addition, in FIG. 6 to FIG. 8, "Prebake" is a spectrum of a film subjected to heat treatment only for prebaking, and "130C" is a film which is heated at 130 ° C for 5 minutes after prebaking. The spectrogram, "200C", is a spectrum of a film which was further heated at 200 ° C for 5 minutes after prebaking.

As shown in Fig. 6, the photosensitive resin composition of the present invention sufficiently absorbs light having a wavelength of, for example, 700 nm. Further, even when heating at 200 ° C, the change in the absorption spectrum is small, and the heat resistance is excellent.

On the other hand, in the photosensitive composition of Comparative Example 1, the solubility of the comparative compound 1 in the solvent was low, and as shown in FIG. 7, light having a wavelength of 700 nm could not be absorbed. Further, the heat resistance is low, and the absorption disappears due to heating at 130 ° C or higher.

Further, as shown in FIG. 8, the photosensitive composition of Comparative Example 2 showed an H-association peak at a wavelength of around 600 nm, and the absorption at a wavelength of 700 nm was small. Further, at the time of heating, peaks in the vicinity of 680 nm and 600 nm fluctuated.

(Synthesis Example 4) Synthesis of Compound C-15

1.7 g of the compound 2 and 3.0 g of the compound 3 were added to 10 ml of acetic anhydride, and the mixture was stirred under heating at 120 ° C for 1 hour. Then, ethyl acetate was added to the reaction solution, and the precipitated solid was separated by filtration, and 1.7 g of the compound 2, diazabicycloundecene 0.5 ml, and 60 ml of acetonitrile were added to the obtained filtrate, and the mixture was stirred at room temperature. In the hour, precipitates were obtained by filtration. Then, 0.4 g of the obtained solid was dissolved in 100 ml of methanol, and 0.5 g of sodium acetate was added thereto, and the mixture was stirred at room temperature for 2 hours, and then the obtained solid was filtered to obtain the object C-15. The yield was 45% and the maximum absorption wavelength was 622 nm in dimethyl hydrazine (DMSO).

<Evaluation of heat resistance and light resistance>

0.5 parts by mass of the compound C-15 was dissolved in 69.5 parts by mass of ion-exchanged water, and further, 30.0 parts by mass of a 10% by mass aqueous solution of gelatin was added and stirred to prepare a resin composition.

The obtained resin composition was applied onto a glass substrate using a spin coater (manufactured by Sanken Co., Ltd.) to form a coating film. Further, the thickness of the coating film was adjusted so as to be 0.2 μm. Then, the coating film was subjected to heat treatment for 120 seconds using a hot plate at 100 °C.

The results of heat resistance and light resistance test of the obtained film by the same method as in Example 1 are shown in Table 7.

According to the results, the compound C-15 was excellent in heat resistance and light resistance.

<Synthesis of copper complexes> <<Synthesis of Polymer A-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 mixture of hexane/ethyl acetate (1/1) 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 polymer A-1 was obtained. The sulfonic acid group content (meq/g) in the polymer was calculated by neutralization titration. Further, the weight average molecular weight (Mw) was measured by gel permeation chromatography.

<<Synthesis of copper complex Cu-1>>

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

<Preparation of Near Infrared Absorbing Composition>

The following components were mixed in the amounts described below to prepare a near-infrared absorbing composition 1.

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

. The engineering plastic copper complex Cu-1: 30 parts by mass

. Compound I-17: 3 parts by mass

. The following curable compound A: 70 parts by mass

. The following surfactant A: 0.4 parts by mass

. Solvent (water): 50 parts by mass

. Solvent (PGMEA): 50 parts by mass

Hardening Compound A: The following compound (Mw: 24,000)

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

Copper complex A was synthesized as follows.

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

<Production of near-infrared cut filter>

A photoresist is applied onto the glass substrate, and patterned by a lithography method to form a partition wall of the photoresist to form a dropping region of the near-infrared absorbing composition. 3 ml of the near-infrared absorbing composition 1 was added dropwise. The substrate with a coating film was allowed to stand at room temperature for 24 hours, and after drying, the coating film thickness was evaluated, and the film thickness was 191 μm. It was confirmed that the obtained near-infrared absorption filter has a transmittance of 90% or more over the entire wavelength range of 450 nm to 550 nm, and a transmittance of 10% or less at a wavelength of 680 nm.

In the preparation of a near-infrared absorbing composition, even if the compound is When I-17 is changed to the compound I-21, the compound I-22 or the compound C-15, the same excellent effect as the near-infrared absorption cut filter using the near-infrared absorbing composition 1 can be obtained. In addition, even if the compound I-17 is changed to Japan In the case of D-1 to D-139 described later in paragraph 0049 of JP-A-2009-263614, the same excellent effect as the near-infrared absorption cutoff filter using the near-infrared absorbing composition 1 can be obtained.

In the preparation of a near-infrared absorbing composition, even a copper complex When A is changed to a copper complex (17 types) having a sulfonic acid compound as a ligand, the same excellent effect as that of the near-infrared absorption cut filter using the near-infrared absorbing composition 1 can be obtained.

In the preparation of the near-infrared absorbing composition, 5 parts by mass are further added Polymeric compound. As the polymerizable compound, the following compounds were used. KAYARAD D-330, KAYARAD D-320, KAYARAD D-310, KAYARAD DPHA, KAYARAD DPCA -20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above, manufactured by Nippon Chemical Co., Ltd.), M-305 , M-510, M-520, M-460 (manufactured by Toago), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR-494 (manufactured by Shado Co., Ltd.), Denacol EX-212L ( Changchun Huacheng (manufacturing), JER-157S65 (manufactured by Mitsubishi Chemical Corporation). That is, in the case of these cases, the same excellent effect as the near-infrared absorption cutoff filter using the near-infrared absorbing composition 1 can be obtained.

In the preparation of the near-infrared absorbing composition, even if the interface is active Agent A was changed to Megafac F171 (made by Di Aisheng (share)), Surfynol 61 (made by Rixin Chemical Co., Ltd.) or Toray Silicone (SF) 1010 (Dongli Dow Corning) In the case of (manufacturing), it is possible to obtain the same excellent effect as the near-infrared absorption cutoff filter using the near-infrared absorbing composition 1.

10‧‧‧ camera module

11‧‧‧ Solid-state imaging components

12‧‧ ‧ flattening layer

13‧‧‧Near-infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧Lens Holder

16‧‧‧Photographic components

17‧‧‧Color Filter

18‧‧‧Microlens

Claims (19)

A near-infrared cut filter comprising a near-infrared absorbing material having a film thickness of 300 μm or less, a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm, and a light transmittance of 10% or less at a wavelength of 680 nm. The near-infrared cut filter according to claim 1, wherein the near-infrared absorbing material contains a first near-infrared absorbing material and a second near-infrared absorbing material, and the first near-infrared absorbing material is a copper compound. The second near-infrared absorbing material is a compound having a maximum absorption wavelength in a wavelength of 650 nm to 750 nm. The near-infrared cut filter according to the first or second aspect of the invention, which comprises the compound represented by the following formula (1) as the near-infrared absorbing material; In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms; Formula (2), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, the wavy line represents the general formula (1) The link. The near-infrared cut filter according to claim 3, wherein the group represented by the formula (2) is represented by the following formula (3) or (4); In the formula (3) and the formula (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, and R ¹² represents a substituent. When m is 2 or more, R ¹² may be bonded to each other to form a ring, and X represents The nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer of 0 to 4, and the wavy line indicates a point of attachment to the formula (1). The near-infrared cut filter according to the third aspect of the invention, wherein R ¹ in the formula (1) is an alkyl group having one or more halogen atoms or an aryl group having one or more halogen atoms. The near-infrared cut filter according to claim 1 or 2, which contains a copper compound as the near-infrared absorbing material, the copper compound being selected from a phosphorus-containing copper complex and a copper sulfonate. At least one of a complex and a copper carboxylate complex. The near-infrared cut filter according to the first or second aspect of the invention, which comprises the compound represented by the following formula (A) as the near-infrared absorbing material; In the general formula (A), Z ¹ and Z ² are each independently a non-metal atomic group of a nitrogen-containing heterocyclic ring forming a condensable ring of 5 or 6 members, and R ¹ and R ² each independently represent an aliphatic group or An aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are each independently 0 or 1. When a site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c Indicates the number necessary for obtaining charge balance. When the portion represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents the number necessary for obtaining charge balance, and Cy in the formula When the charge of the indicated portion is neutralized in the molecule, X ¹ does not exist. The near-infrared cut filter according to the first or second aspect of the invention, wherein the film thickness is 200 μm or less. The near-infrared cut filter according to claim 1 or 2, wherein the light transmittance in the range of wavelengths of 400 nm to 575 nm is 85% or more. The near-infrared cut filter according to the first or second aspect of the invention, wherein the light transmittance in the range of 450 nm to 550 nm is 90% or more. The near-infrared cut filter according to claim 1 or 2, wherein the light transmittance in the range of 700 nm to 1100 nm is 20% or less. The near-infrared cut filter according to the first or second aspect of the invention, wherein the light transmittance in the range of 800 nm to 900 nm is 10% or less. A near-infrared ray absorbing composition containing a near-infrared absorbing material and having a film thickness of 300 μm or less and having a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm and a light transmittance of 10% at a wavelength of 680 nm the following. The near-infrared ray absorbing composition according to claim 13, which comprises a copper complex compound having at least one selected from the group consisting of a sulfonic acid and a carboxylic acid as a ligand, and is selected from the following formula (1) At least one of the compound represented by the compound and the compound represented by the following formula (A) is used as the near-infrared absorbing material; In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms; In the formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a formula (1) Joint site; In the general formula (A), Z ¹ and Z ² each independently represent a non-metallic atomic group forming a nitrogen-containing heterocyclic ring or a fused ring of 5 to 6, R ¹ and R ² each independently represent an aliphatic group or an aromatic group, L ¹ represents a methine group contains an odd number of methine chains, a and b are independently 0 or 1, when the portion of the formula is represented by Cy cationic unit, X ¹ represents an anion, C Indicates the number necessary for obtaining charge balance. When the portion represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents the number necessary for obtaining charge balance, and Cy in the formula When the charge of the indicated portion is neutralized in the molecule, X ¹ does not exist. A photosensitive resin composition containing a compound represented by the following formula (1); In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms; Formula (2), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, the wavy line represents the general formula (1) The link. A cured film obtained by curing the photosensitive resin composition according to item 15 of the patent application. a compound represented by the following formula (1); In the formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following formula (2), and R ¹ represents an alkyl group having one or more halogen atoms, and has 1 An aryl group having more than one halogen atom or a heterocyclic group having one or more halogen atoms; Formula (2), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, the wavy line represents the general formula (1) The link. A camera module having a solid-state imaging device and a near-infrared cut filter according to any one of claims 1 to 12, which is disposed on a light receiving side of the solid-state imaging device. A method of manufacturing a camera film set, which is a method of manufacturing a camera module according to claim 18, and having a near-infrared absorbing composition applied to a light-receiving side of the solid-state image sensor, thereby forming a near-infrared ray cutoff In the step of the filter, the near-infrared ray absorbing composition contains a near-infrared absorbing material, and a light transmittance in a range of 450 nm to 550 nm in a range of a film thickness of 300 μm or less is 85% or more, and a light transmittance of 680 nm is transmitted. The rate is below 10%.