TWI660036B - 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

The present invention provides a near-infrared cut-off filter, 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 capable of obtaining a camera image with good image quality. The near-infrared cut filter of the present invention contains a near-infrared absorbing substance, has a film thickness of 300 μm or less, and has 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 in a wavelength of 680 nm.

Description

Near-infrared cut-off filter, near-infrared absorbing composition, photosensitive Resin composition, cured film, compound, camera module and method for manufacturing camera module

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 for manufacturing a camera module.

In recent years, Charge-Coupled Device (CCD) has been used as a solid-state imaging device for color images in video cameras, digital still cameras, and mobile phones with camera functions. ) Or a complementary metal-oxide semiconductor (Complementary Metal-Oxide-Semiconductor, CMOS) image sensor. The solid-state imaging device uses a silicon photodiode that has sensitivity to near-infrared in its light-receiving part. Therefore, it is necessary to correct the luminosity. In most cases, a near-infrared cut-off filter (hereinafter also referred to as IR Cut-off filter).

As a material of the near-infrared cut filter, Patent Document 1 discloses An infrared blocking film containing an infrared blocking resin which is a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof with a compound having an ethylenically unsaturated bond The copolymer is made by adding a metal compound.

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

In addition, Patent Document 3 discloses a color filter using a squarylium compound.

[Prior Art Literature]

[Patent Literature]

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

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

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

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

Therefore, an object of the present invention is to provide a near-infrared cut-off 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 camera images and the like with good image quality. Manufacturing method.

Specifically, the above-mentioned problem was solved by the following means <1>, preferably means <2> to means <19>.

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

<2> The near-infrared cutoff filter according to <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, and the second near-infrared absorbing material is The infrared absorbing substance is a compound having a maximum absorption wavelength within 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 general formula (1) as a near-infrared absorbing substance;

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

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection.

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

In the general formulae (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group, or an aralkyl group, R ¹² represents a substituent group, and when m is 2 or more, R ¹² may be connected to each other to form a ring, and X represents A 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 a wavy line represents a connection site with the general formula (1).

<5> The near-infrared cut filter according to <3> or <4>, wherein R ¹ in the general formula (1) is an alkyl group having one or more halogen atoms or an aryl group having one or more halogen atoms .

<6> The near-infrared cut filter according to any one of <1> to <5>, which contains a copper compound as a near-infrared absorbing substance, and the copper compound is selected from a copper complex containing phosphorus and copper sulfonate At least one of a complex and a copper carboxylate complex.

<7> The near-infrared cut filter according to any one of <1> to <6>, which contains a compound represented by the following general formula (A) as a near-infrared absorbing substance;

In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist.

<8> The near-infrared cut filter according to any one of <1> to <7>, wherein the film thickness is 200 μm or less.

<9> The near-infrared cut filter according to any one of <1> to <8>, wherein a light transmittance in a range of a wavelength of 400 nm to 575 nm is 85% or more.

<10> The near-infrared cut filter according to any one of <1> to <9>, wherein a light transmittance in a range of a wavelength of 450 nm to 550 nm is 90% or more.

<11> The near-infrared cut filter according to any one of <1> to <10>, wherein a light transmittance in a range of a wavelength of 700 nm to 1100 nm is 20% or less.

<12> The near-infrared cut filter according to any one of <1> to <11>, wherein a light transmittance in a range of a wavelength of 800 nm to 900 nm is 10% or less.

<13> A near-infrared absorbing composition containing a near-infrared absorbing substance and forming a film having a film thickness of 300 μm or less When the light transmittance is in the range of 450 nm to 550 nm, the light transmittance is 85% or more, and the light transmittance is 680 nm. It is below 10%.

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

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

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection site; general formula (A) [Chem. 8]

In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge at the indicated site is neutralized in the molecule, x ¹ does not exist.

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

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

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection.

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

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

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

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection.

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

<19> A method for manufacturing a camera film set, which is a method for manufacturing a camera module according to <18>, and further comprising applying a light-receiving side of a solid-state imaging element as described in <13> or <14>. The step of forming a near-infrared cut-off filter by absorbing the infrared composition.

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

In addition, by containing a compound represented by the general formula (1) and / or a compound represented by the general formula (A) The compound shown as a near-infrared absorbing substance can also provide a near-infrared cut-off filter excellent in heat resistance.

10‧‧‧ Camera Module

11‧‧‧ solid-state imaging element

12‧‧‧ flattening layer

13‧‧‧Near infrared cut-off filter

14‧‧‧ camera lens

15‧‧‧ lens holder

16‧‧‧ camera element

17‧‧‧Color Filter

18‧‧‧ micro lens

19‧‧‧ UV. Infrared light reflecting film

20‧‧‧ transparent substrate

21‧‧‧Near-infrared absorbing layer

22‧‧‧Anti-reflective layer

FIG. 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.

FIG. 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.

FIG. 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 diagram showing an absorption spectrum (DMSO) of Compound I-17.

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

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

8 is a spectrum diagram showing a light transmittance of a film obtained using the photosensitive resin composition of Comparative Example 2. FIG.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in the specification of this application, "~" refers to the lower limit and upper limit including the numerical values described before and after. Meaningful use of limits.

In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to acryl and Methacrylfluorenyl. In addition, in this specification, "single body" and "monomer" have the same meaning. Monomers are compounds that are different from oligomers and polymers and have a weight average molecular weight of 2,000 or less.

In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a singular body or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In the description of the group (atomic group) in this specification, the descriptions that are not substituted and unsubstituted include a group (atomic group) having no substituent and also include a group (atomic group) having a substituent.

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

The near-infrared rays are light (electromagnetic waves) having a wavelength range of 700 to 2500 nm.

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

In this specification, a weight average molecular weight and a number average molecular weight are defined as the polystyrene conversion value measured by the gel permeation chromatography (GPC). In this specification, for example, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (Tosoh (Manufactured, 6.0 mm ID × 15.0 cm) as a column, and a 10 mmol / L lithium bromide N-methyl pyrrolidinone (NMP) solution was used as a washing solution.

<Near-infrared absorbing composition>

The near-infrared absorbing composition of the present invention contains a near-infrared absorbing substance. The near-infrared absorbing substance preferably contains a compound having a maximum absorption wavelength within a wavelength of 650 nm to 750 nm, more preferably a cyanine compound, a pyrrolopyrrole compound, and a squarnoinium compound, further preferably a compound selected from It is particularly preferred that at least one of the compound represented by (1) and the compound represented by the following general formula (A) contains a compound represented by the following general formula (1).

<< Near-infrared absorbing substance >>

<<< Compound represented by General Formula (1) >>>

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

[Chemical 14]

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection.

R ¹ in the general 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 atomic alkyl group or the aryl group having one or more halogen atoms is particularly preferably an alkyl group having one or more halogen atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred. The fluorine atom reduces the nucleophilicity (in other words, increases the stability of the anion) of the adjacent anion by the electron-drawing effect. Therefore, when it is a fluorine atom, for example, it is considered that it is difficult to decompose the compound represented by the general formula (1) due to anions during heating, and heat resistance is particularly improved. In addition, as the number of fluorine atoms increases, the nucleophilicity of the anion decreases, so the heat resistance is further improved.

The number of halogen atoms contained in R ¹ is one or more, and preferably 50% or more of hydrogen atoms bonded to carbon atoms of the group (alkyl, aryl, heterocyclic group) represented by R ¹ are substituted. It is 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, even more preferably from 1 to 8, and particularly preferably from 1 to 3. The alkyl group may be any of linear, branched, and cyclic, and more preferably linear or branched. Branch.

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

The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. In addition, the heterocyclic group is preferably a monocyclic or condensed ring, preferably a monocyclic or condensed ring having a condensation number of 2 to 8, and more preferably a monocyclic or condensed ring having a condensation number of 2 to 4. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms is preferably 1 to 3, and more preferably 1 to 2.

R ^{1 is} preferably a perfluoroalkyl group or a perfluoroaryl group, and particularly preferably a perfluoroalkyl group. The term “perfluoroalkyl group” refers to a group in which all the hydrogen atoms bonded to the carbon atoms constituting the alkyl group are replaced with fluorine atoms. The perfluoroaryl group refers to a group in which all hydrogen atoms bonded to carbon atoms constituting the aryl group are substituted with fluorine atoms.

A ¹ and A ² in the general formula (1) each independently represent an aryl group, a heterocyclic group, or a group represented by the general formula (2), and is preferably a group represented by the general 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 include phenyl and naphthyl. 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. In addition, the heterocyclic group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 8, more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4, and more preferably a monocyclic ring. Ring or condensed ring having a condensation number of 2 or 3. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom and a sulfur atom are preferred. The number of heteroatoms is preferably 1 to 3, and more preferably 1 to 2. Specifically, a heterocyclic group derived from a monocyclic or polycyclic aromatic ring 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 is exemplified.

Aryl and heterocyclic groups may have a substituent. Examples of the substituent include the following.

Examples include: a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably 1 carbon number) ~ 30 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, third butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl); Cycloalkyl (preferably substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, and polycycloalkyl, for example, bicycloalkyl (preferably carbon) 5 to 30 substituted or unsubstituted bicycloalkyl, for example, bicyclo [1.2.2] heptane-2-yl, bicyclo [2.2.2] octane-3-yl), or tricycloalkyl Polycyclic structure group. Preferred are monocyclic cycloalkyl and bicycloalkyl, especially monocyclic cycloalkyl); linear or branched alkenyl (linear or branched substituted or unsubstituted) Alkenyl is preferably an alkenyl having 2 to 30 carbon atoms, for example, vinyl, allyl, isoprenyl, geranyl, oleyl, etc .; cycloalkenyl (preferably 3 carbons) ~ 30 substituted or unsubstituted cycloalkenyl, for example, 2-cyclopentene-1- 2, 2-cyclohexen-1-yl, polycyclic alkenyl, for example, bicyclic alkenyl (preferably substituted or unsubstituted bicyclic alkenyl having 5 to 30 carbon atoms, for example, bicyclic [2.2.1] Hept-2-en-1-yl, bicyclic [2.2.2] oct-2-en-4-yl) or tricyclic alkenyl, particularly preferably monocyclic cycloalkenyl); alkynyl (preferably carbon 2-30 substituted or unsubstituted alkynyl, for example, Ethynyl, propargyl, trimethylallylethynyl); aryl (preferably substituted or unsubstituted aryl having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl , M-chlorophenyl, o-hexadecylaminoaminophenyl); heterocyclic (preferably 5 to 7 members substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, mono A ring or condensed heterocyclic group is more preferably a heterocyclic group in which the ring constituent atom is selected from a carbon atom, a nitrogen atom, and a sulfur atom and has a hetero atom of at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, Furthermore, a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms is preferred. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidyl, 2- Benzothiazolyl); cyano; hydroxyl; nitro; carboxy; alkoxy (preferably substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, for example, methoxy, ethoxy, Isopropoxy, tertiary 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- Amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecylaminophenoxy); silyloxy (preferably 3 to 20 carbons) Silyloxy, for example, trimethylsilyloxy, third butyldimethylsilyloxy); heterocyclicoxy (preferably substituted or unsubstituted carbon having 2 to 30 carbon atoms) Heteroepoxy And the heterocyclic part is preferably the heterocyclic part described in the heterocyclic group, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); fluorenyloxy 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 methylamino, ethyl Fluorenyloxy, trimethylacetoxy, stearylfluorenyl, benzamyloxy, p-methoxyphenylcarbonyloxy); carbamoyloxy (preferably 1 to 30 carbon atoms) Substituted or unsubstituted carbamoyloxy, such as N, N-dimethylaminoformamyloxy, N, N-diethylaminoformamyloxy, morpholinylcarbonyloxy Group, N, N-di-n-octylaminocarbonyloxy group, N-n-octylamine formamyloxy group; alkoxycarbonyloxy group (preferably substituted or unsubstituted carbon number 2-30) Substituted alkoxycarbonyloxy, for example, methoxycarbonyloxy, ethoxycarbonyloxy, third 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 (preferably amine, substituted or unsubstituted with 1 to 30 carbon atoms) Alkylamino groups, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, heterocyclic amino groups having 0 to 30 carbon atoms, for example, amino groups, methylamino groups, dimethylamino groups, Aniline, N-methyl-aniline, diphenylamino, N-1,3,5-triazin-2-ylamino); fluorenylamino (preferably with 1 to 30 carbon atoms) Substituted or unsubstituted alkylcarbonylamino groups, substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, for example, Formamylamino, ethanoylamino, trimethylethylamino, laurylamino, benzylamino, 3,4,5-tri-n-octyloxyphenylcarbonyl Amine group); aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylamino Carbonylamino, N, N-diethylaminocarbonylamino, morpholinylcarbonylamino); alkoxycarbonylamino (preferably substituted or unsubstituted alkoxy having 2 to 30 carbon atoms) Carbonylamino, for example, methoxycarbonylamino, ethoxycarbonylamino, tertiary butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonyl Amine); aryloxycarbonylamino (preferably substituted or unsubstituted aryloxycarbonylamino having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamine Group, m-n-octyloxyphenoxycarbonylamino group); aminesulfonylamino group (preferably substituted or unsubstituted aminesulfonylamino group having 0 to 30 carbon atoms, for example, amine Sulfonylamino, N, N-dimethylaminosulfonylamino, N-n-octylaminosulfonyl Amine group); alkylsulfonylamino group or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, 6 to 30 carbon atoms) Substituted or unsubstituted arylsulfonylamino groups, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorobenzene Sulfosulfanylamino, p-methylphenylsulfonylamino); mercapto; alkylthio (preferably substituted or unsubstituted alkylthio 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-thio) Chlorophenylthio, m-methoxyphenylthio); heterocyclic thio (preferably substituted or unsubstituted heterocyclic thio having 2 to 30 carbon atoms, and the heterocyclic part is preferably the hetero The heterocyclic part described in the cyclic group, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio); sulfamoyl group (preferably a carbon number of 0 to 30) Substituted or unsubstituted aminesulfonyl, for example, N-ethylaminesulfonyl, N- (3-dodecyloxypropyl) aminesulfonyl, N, N-dimethylaminesulfonyl Fluorenyl, N-ethylfluorenylamine sulfonyl, N-benzylaminosulfonyl, N- (N'-phenylaminomethylsulfonyl) aminosulfonyl); sulfo; alkylsulfinyl Fluorenyl or arylsulfinylfluorenyl (preferably substituted or unsubstituted alkylsulfinyl having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl having 6 to 30 carbon atoms Fluorenyl, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl); alkylsulfinyl or arylsulfinyl (compared to good 1 to 30 carbon substituted or unsubstituted alkylsulfonyl groups, 6 to 30 carbon substituted or unsubstituted arylsulfonyl groups, for example, methylsulfonyl, ethylsulfonyl Group, phenylsulfonyl, p-methylphenylsulfonyl); fluorenyl (preferably methylamidino, substituted or unsubstituted alkylcarbonyl having 2 to 30 carbon atoms, 7 to 30 carbon atoms) Substituted or unsubstituted arylcarbonyl groups, such as ethenyl, trimethylethenyl, 2-chloroethenyl, stearyl, benzyl, p-n Octyloxyphenylcarbonyl); aryloxycarbonyl (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m Nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl); alkoxycarbonyl (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms, for example, methoxy Carbonyl, ethoxycarbonyl, third butoxycarbonyl, n-octadecyloxycarbonyl); carbamate (preferably substituted or unsubstituted carbamate having 1 to 30 carbon atoms, For example, carbamate, N-methylcarbamate, N, N-dimethylcarbamate, N, N-di-n-octylamine carbamate, N- (methylsulfamethyl) ) Carboxamido); arylazo or heterocyclic azo (preferably substituted or unsubstituted aryl azo having 6 to 30 carbon atoms, substituted or Unsubstituted heterocyclic azo group (the heterocyclic portion is preferably the heterocyclic portion described in the heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethyl Thio-1,3,4-thiadiazol-2-ylazo); fluorenimine (preferably substituted or unsubstituted carbon number 2-30) Substituted fluorenimine, for example, N-succinimide, N-phthalimide, imino); phosphino (preferably substituted or unsubstituted phosphino having 2 to 30 carbon atoms) , For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino); phosphinyl (preferably substituted or unsubstituted phosphinyl with 2-30 carbon atoms, for example, Phosphinyl, dioctyloxyphosphino, diethoxyphosphino); phosphinyloxy (preferably substituted or unsubstituted phosphinyloxy having 2 to 30 carbon atoms, For example, diphenoxyphosphinooxy, dioctyloxyphosphinooxy); Phosphophosphinoamino (preferably substituted or unsubstituted phosphphosphinoamino having 2 to 30 carbon atoms, for example, dimethoxyphosphinoamino, dimethylaminophosphinoamino) ); Silyl group (preferably substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl group, third butyldimethylsilyl group, phenyldimethylsilyl 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 fluorenylamino group.

The halogen atom is preferably a chlorine atom.

The carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and most preferably 1 to 4. The alkyl group is preferably linear or branched.

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 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 8. The alkyl group is preferably linear or branched, and more preferably linear.

The fluorenylamino group is preferably a group represented by -NR ¹⁰² -C (= O) -R ¹⁰³ . R ¹⁰² represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. R ¹⁰³ represents an alkyl group. The carbon number of the alkyl group represented by R ¹⁰² and R ¹⁰³ is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 4.

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

Next, a group represented by General Formula (2) represented by A ¹ and A ² will be described.

In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection.

In the general formula (2), R ² represents an alkyl group, an alkenyl group, or an aralkyl group, and is preferably an alkyl group.

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

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

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

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

In the general formula (2), the nitrogen-containing heterocyclic ring formed by Z ^{1 is} preferably a 5-membered ring or a 6-membered ring. In addition, the nitrogen-containing heterocyclic ring is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring of 2 to 4 and further preferably Condensation rings with a condensation number of 2 or 3. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to a nitrogen atom. The nitrogen-containing heterocyclic ring may have a substituent. Examples of the substituent include substituents which the aryl group or heterocyclic group may have, and preferred ranges are also the same. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and a fluorenylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. The alkyl group is preferably linear or branched.

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

In the general formulae (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group, or an aralkyl group, R ¹² represents a substituent group, and when m is 2 or more, R ¹² may be connected to each other to form a ring, and X represents A 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 a wavy line represents a connection site with the general formula (1).

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

R ¹² in the general formula (3) and the general formula (4) represents a substituent. Examples of the substituent include substituents which the aryl group or heterocyclic group may have, and preferred ranges are also the same. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and a fluorenylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. The alkyl group is preferably linear or branched.

When m is 2 or more, R ¹² may be connected to each other to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or heterocyclic. The linking group when the substituents are connected 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 combinations thereof. Divalent link base link in the group. For example, R ^{12 is} preferably connected to each other to form a benzene ring.

X in the general 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. Examples of the substituent include substituents which the aryl group or heterocyclic group may have. For example, an alkyl group is mentioned. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5, particularly preferably from 1 to 3, and most preferably 1. The alkyl group is preferably linear or branched, and particularly preferably linear.

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

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

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

Specific examples of the compound represented by the general formula (1) include, but are not limited to, the compounds described below. In the following, R ¹ , A ^1, and A ² correspond to the general formula (1), respectively. The wavy lines in the groups shown by A ¹ and A ² represent the connection sites with the general formula (1).

[table 3]

[Table 4]

[table 5]

The near-infrared absorbing composition of the present invention preferably contains 5 to 90% by mass of a compound represented by the general formula (1) with respect to the total solid content of the near-infrared absorbing composition. 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, and more preferably 80% by mass or less.

Moreover, it is preferable to contain the compound represented by General formula (1) from 0.01 mass part-50 mass parts with respect to 100 mass parts of copper compounds mentioned 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, and more preferably 30% by mass or less.

By setting it as such a range, it is possible to obtain a near-infrared cut-off filter that has good blocking properties in the desired range and cuts off infrared rays. For example, it is possible to obtain near-infrared cut-offs with spectral characteristics of a film thickness of 300 μm or less, a spectral characteristic of 85% or more in a wavelength range of 450 nm to 550 nm, and 10% or less of a light transmittance of 680 nm filter.

<<< Compound represented by General Formula (A) >>>

In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist.

In the general formula (A), Z ¹ and Z ² each independently represent a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring.

The nitrogen-containing heterocyclic ring may be condensed with other heterocyclic rings, aromatic rings or aliphatic rings. Nitrogen The ring is preferably a 5-member ring. Further preferably, the 5-membered nitrogen-containing heterocyclic ring is condensed with a benzene ring or a naphthalene ring. Specific examples of the nitrogen-containing heterocyclic ring include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazocarbazole ring, an oxazodibenzofuran ring, a thiazole ring, Benzothiazole ring, naphthothiazole ring, pseudoindole ring, benzo pseudoindole ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furanopyrrole Ring, indoxazine ring, imidazoquinoxaline ring, quinoxaline ring and the like, preferably a quinoline ring, a pseudoindole ring, a benzo pseudoindole ring, a benzoxazole ring, a benzothiazole ring, The benzimidazole ring is particularly preferably an indole ring, a benzothiazole ring, or 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. In addition, when R ¹² of -COOR ¹² is a hydrogen atom (ie, a carboxyl group), the hydrogen atom may be dissociated (ie, a carbonate group) or may be in a salt state. In addition, when R ²⁴ of -SO ₂ OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated (that is, a sulfonate group) or 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.

Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group. These groups may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amine group, and the like. A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. The hydrogen atoms of the carboxyl group and the sulfo group may be dissociated or may be in a salt state.

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

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

The alkynyl group may be cyclic or chain. The chain alkynyl group may have a branch. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and most preferably 2 to 8. Examples of the alkynyl group include ethynyl and 2-propynyl.

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

In the present invention, the aromatic group includes an aryl group. The aryl group may have a substituent. Examples of the substituent include substituents which the aliphatic group may have, and preferred ranges are also the same.

The carbon number of the aryl group is preferably 6 to 25, more preferably 6 to 15, and most preferably 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 4-carboxyphenyl, 4-acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl, and 3,5- Dicarboxyphenyl, 4-methanesulfonamidophenyl, and 4-butsulfonamidophenyl.

In the present invention, the heterocyclic group may have a substituent. Examples of the substituent include substituents which the aliphatic group may have, and preferred ranges are also the same.

The heterocyclic ring of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring may be a monocyclic ring or a condensed ring. Examples of the heterocyclic ring include a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, and a carbazole Ring, phenothiazine ring, phenoxazine ring, indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and 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. Examples of the aromatic group include an aryl group. Examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group, and aryl group include those described in the above-mentioned substituents, and preferred ranges are also the same. Alkyl, alkenyl, alkynyl, aralkyl, and aryl groups may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amine group, and the like. A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. The hydrogen atoms of the carboxyl group and the sulfo group may be dissociated or may be in a salt state.

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

The methine group may 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 which the nitrogen-containing heterocyclic ring of Z ¹ and Z ² may have. In addition, two substituents of a methine chain may be bonded to form a 5-membered ring or a 6-membered ring.

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

In the general formula (A), when the site represented by Cy in the formula is a cation site, X ¹ represents an anion, and c represents the number necessary for achieving charge balance. Examples of the anions include: halide ions ^{(Cl -, Br -, I} -), p-toluenesulfonate ion, ethyl sulfate ion, PF ₆ ^-, BF ₄ ^- or ClO ₄ ^-, tris (haloalkyl sulfo acyl) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetracyanoquinodimethane Borate anions, etc.

In the general formula (A), when the site represented by Cy in the formula is an anion site, X ¹ represents a cation, and c represents the number necessary to achieve 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, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenyl, and the like. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecenyl are preferred.

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

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

In formula (1A) and formula (1B), R ^1A , R ^2A , R ^1B, and R ^2B each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group, and L ^1A and L ^1B are each independently Represents an methine chain containing an odd number of methine groups, Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 or -CR ^X2 R ^X3- , and each of R ^X1 , R ^X2 and R ^X3 Independently represent a hydrogen atom or an alkyl group, and V ^1A , V ^2A , V ^1B, and V ^2B each independently represent a halogen atom, cyano, nitro, alkyl, alkenyl, alkynyl, aralkyl, aryl, hetero Aryl, -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 can also form condensed rings, and R ¹⁰ ~ R ²⁷ are each independently when a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, R ¹² -COOR ^12, R is a hydrogen atom and -SO ₂ oR ^{24 24} is a hydrogen atom, a hydrogen atom It can be dissociated or it can be in the state of salt, m1 and m2 each independently represent 0 ~ 4, when the position represented by Cy in the formula is yang When subsections, 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 charge balance necessary for obtaining When the charge of the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B have the same meanings as the alkyl, alkenyl, alkynyl, aralkyl and aryl groups described in R ¹ and R ² of the general formula (A), The preferred range is the same. These groups may be unsubstituted or substituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, an amine group, and the like. A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. The hydrogen atoms of the carboxyl group and the sulfo group may be dissociated or may be in a salt state.

When R ^1A , R ^2A , R ^1B and R ^{2B each} 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- , and preferably -NR ^X1- .

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

L ^1A and L ^{1B have the} same meaning as L ¹ of the general formula (A), and the preferred ranges are also the same.

The ranges indicated in the groups represented by V ^1A , V ^2A , V ^1B and V ^2B and the substituents which the nitrogen-containing heterocyclic ring of Z ¹ and Z ² of the general formula (A) may have have the same meaning, and a preferred range The same.

m1 and m2 each 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 general formula (A) are shown below. In the following tables, Me represents methyl, Et represents ethyl, Bu represents butyl, Bn represents benzyl, Ph represents phenyl, PRS represents C ₃ H ₆ SO ^3- , and BUS represents C ₄ H ₉ SO ^3- .

[Chemical 20]

[TABLE 6]

[TABLE 7]

[Chemical 21]

For compounds represented by general formula (A), please refer to FM Harmer's "Heterocyclic Compounds-Cyanine Dyes and Related Compounds" (John Wiley & Son Sons)-New York, London, 1964) and DM DMSturmer, "Heterocyclic Compounds-Specialtopics in heterocyclic chemistry" (Chapter 18, Section 14, pages 482-515, John Wiley and his sons) Wiley & Sons)-New York, London, 1977), "Rodd's Chemistry of Carbon Compounds" (2nd Edition, Volume IV, Part B, published in 1977, Chapter 15, 369 to 422 pages, published by Elsevier Science Publishing Company Inc. (New York), Japanese Patent Laid-Open No. 6-313939, and Japanese Patent Laid-Open No. 5-88293.

<<< solid dispersion >>>

Among the compound represented by the general formula (1) and the compound represented by the general formula (A) (hereinafter, also referred to as a pigment compound), there are compounds that form an association when dissolved in water. It is preferable to add gelatin or a salt (for example, barium chloride, potassium chloride, sodium chloride, calcium chloride) to an aqueous solution of a pigment compound to form an association compound. The method of adding gelatin to the aqueous solution of a pigment compound is more preferable.

The association of the pigment compound may be formed as a solid fine particle dispersion of the pigment compound. Regarding solid dispersion, for example, "Pigment Dispersion Technology-Use of Surface Treatment and Dispersant and Evaluation of Dispersibility-" issued by Technical Information Association Co., Ltd., "Pigment Encyclopedia Dictionary" issued by Asakura Bookstore Co., Ltd., and Technical Information Association The latest "Pigment Dispersion Practice Techniques and Cases" issued by the company is described in detail. In order to prepare a solid fine particle dispersion, a known disperser can be used. Examples of dispersing machines include ball mills, vibration ball mills, planetary ball mills, sand mills Machine, rubber mill, jet mill and roller mill. The dispersing machine is described in Japanese Patent Laid-Open No. 52-92716 and International Publication No. 88/074794. A vertical 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). Preferably, a surfactant is used. As the surfactant, an anionic surfactant (described in Japanese Patent Laid-Open No. 52-92716 and International Patent 88/074794) can be preferably used. An anionic polymer, a nonionic surfactant, or a cationic surfactant can also be used as needed.

After dissolving the pigment compound in an appropriate solvent, a poor solvent may be added to obtain a fine powder. In this case, the surfactant may also be used. Alternatively, it is possible to dissolve by adjusting the pH value, and then change the pH value to precipitate microcrystals of the pigment. The microcrystals are also associations of pigment compounds. When the associative pigment compound is fine particles (or microcrystals), the average particle diameter is 1,000 μm or less, preferably 0.001 μm to 100 μm, and more preferably 0.005 μm to 50 μm.

In order to improve the dispersibility of the pigment compound, a conventionally known resin or a surfactant may be added. Examples of commercially available products include phthalocyanine derivatives (commercially available products: EFKA-745 (manufactured by EFKA)), Solsperse 5000 (German ( (Zeneca)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 90 Cationic surfactants such as 95 (produced by Gongrongsha Oil Chemical Industry Co., Ltd.), W001 (produced by Yushang Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene Oleyl ether, polyethylene oxide octylphenyl ether, polyethylene oxide nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Non-ionic interface surfactants; anionic surfactants such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); Efka (EFKA) -46, Efka (47), Efka ( EFKA) -47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above, Morishita Industries ( Stock), Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Disperse-aid ) 9100 (Sannopco (manufactured)) and other polymeric dispersants; Solups 3000 (Solsperse), Solsperse 5000 (Solsperse) 9000, Solu Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000, etc. Sonupas dispersant (manufactured by Zeneca); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeco Pro Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Adeka Pluronic L121, Adeka Pluronic P-123 (manufactured by Asahi Denka Co., Ltd.), and Ionet (manufactured by Sanyo Kasei Co., Ltd.).

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

Further, the graft copolymer having a monomer containing a specific acid amide group and a quaternary ammonium salt monomer residue in the main chain portion described in Japanese Patent Laid-Open No. 10-254133 has a pigment compound. It has excellent effect of microdispersion, so it can be used preferably. By using the graft copolymer, the pigment can be finely dispersed while reducing energy or time consumption, and the dispersed pigment does not agglomerate or settle over time, and dispersion stability can be maintained for a long time. The resins may be used alone or in combination of two or more. The addition amount of the resin is preferably about 1 to 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 substance. 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, and more preferably divalent copper.

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

The copper compound may be a copper compound other than a copper complex, or may be a copper complex, and a copper complex is preferred. As the copper compound, copper or a copper-containing compound can be used. As the copper-containing compound, for example, copper oxide or a copper salt can be used. The copper salt is more preferably copper acetate, copper chloride, copper formate, copper hydroxide, copper stearate, copper benzoate, copper ethylacetate, copper pyrophosphate, copper naphthenate, copper citrate, Copper nitrate, copper sulfate, copper carbonate, copper chlorate, copper (meth) acrylate, copper perchlorate, more 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, and 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 , Copper carboxylate compound, copper phosphinate compound, copper phosphate compound), further preferably copper sulfonate compound, copper carboxylate compound, and copper phosphate compound, and even more preferably copper sulfonate compound and copper carboxylate compound.

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

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

In the formula (A), L represents a ligand coordinated to copper, and X does not exist 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 an alcohol. n1 and n2 each independently represent an integer of 1 to 4.

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

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

Examples of the compound or a salt thereof as a ligand include an organic acid compound or a salt thereof. 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, and amidine. , Sulfonamide, carbamate, urea, alcohol, thiol, etc. Among these, phosphoric acid, phosphate ester, phosphonic acid, phosphonate, phosphinic acid, substituted phosphinic acid, sulfonic acid, and carboxylic acid are more preferable, and phosphate ester, phosphonate, substituted phosphinic acid, and sulfonic acid are more preferable. ,carboxylic acid.

The compound or a salt thereof which becomes a ligand is preferably represented by the following general formula (i).

(In the general 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 general formula (i), R ^{1 is} preferably a hydrocarbon group or an oxyalkylene group, and 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, vinyl, (meth) acrylfluorenyl, epoxy, and oxetan (Alkyl group, etc.), sulfonic acid group, carboxylic acid group, acid group containing phosphorus atom, carboxylic acid ester group (e.g. -CO ₂ CH ₃ ), hydroxyl group, alkoxy group (e.g. methoxy group), amine group, amine methyl group Amidino, carbamoyloxy, haloalkyl (for example, fluoroalkyl, chloroalkyl), and the like. When the hydrocarbon group has a substituent, it may further have a substituent, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.

When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group or an aryl group is preferred, and an aryl group is more preferred. When the hydrocarbon group is divalent, an alkylene group, an alkylene group, or an oxyalkylene group is preferable, and an alkylene group is more preferable. When the hydrocarbon group is trivalent or more, 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 linear, branched, or cyclic. The carbon number of the linear alkyl group and the alkylene group is preferably from 1 to 20, more preferably from 1 to 12, and even 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 even more preferably from 3 to 8. The cyclic alkyl group and the alkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cyclic alkyl group and the alkylene group is preferably 3 to 20, more preferably 4 to 10, and even more preferably 6 to 10.

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

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

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

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

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

Preferred embodiments of the compound containing an acid group or a salt thereof include (1) a compound having at least one of a sulfonic acid group, a carboxylic acid group, and an acid group containing a phosphorus atom, and more preferably (2) a compound having two or more The form of the acid group is more preferably (3) a form having a sulfonic acid group and a carboxylic acid group. These forms are more easily deformed than the structure of the copper complex, so the color value can be further increased, and the near-infrared absorbing ability, that is, the infrared absorbing ability can be more effectively exerted. Furthermore, 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 ligand-forming compound will be described in detail.

<<<< Phosphorous copper complex >>>>

The phosphorus-containing copper complex is not particularly limited as long as it has a ligand containing a phosphorus compound, and copper phosphate complex, phosphate copper complex, copper phosphonate complex, and phosphonic acid are preferred. Copper ester complexes, copper phosphinate complexes, substituted copper phosphinate complexes, more preferably copper phosphate complexes, copper phosphonate complexes, substituted copper phosphinate complexes 组合。 The compound.

<<<<< Phosphate copper complex >>>>>

Phosphate copper complex is a complex containing copper as a central metal and a phosphate compound as a ligand. The ligand-forming phosphate compound is more preferably a compound represented by the following formula (B).

(HO) _n -P (= O)-(OR ² ) _3-n Formula (B)

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

(Wherein R ² represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 1 to 18 carbon atoms or an alkenyl group having 1 to 18 carbon atoms, or -OR ² represents carbon Polyoxyalkyl group having 4 to 100 carbon atoms, (meth) acryloxyalkyl group having 4 to 100 carbon atoms, or (meth) acrylfluorenyl polyoxyalkyl group having 4 to 100 carbon atoms, n represents 1 or 2 )

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

As specific examples of the phosphate compound, for example, paragraphs 0020 to 0025 of Japanese Patent Laid-Open No. 2013-253224 (paragraphs 0020 to 0025 of the corresponding International Publication WO2013 / 168824 pamphlet), and Japanese Patent Laid-Open No. 2001- The descriptions of paragraphs 0041 to 0045 (corresponding to US Patent Application Publication No. 2003/0160217 [0059]) in JP 354945 are incorporated into the description of this application.

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

Copper phosphonate complexes are copper-centered metals and phosphonate compounds Complex The ligand-forming phosphonate compound is more preferably a compound represented by the following formula (E).

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

The compound represented by formula (E) and its salt 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, these groups may also be via a divalent linking group (e.g., alkylene, cycloalkyl, aryl, heteroaryl, -O-, -S-, -CO-, -COO) -, -OCO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group). The monovalent organic group may have a substituent.

The carbon number of the linear or branched alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8.

The cyclic alkyl group may be monocyclic or polycyclic. The carbon number of the cyclic alkyl group is preferably 3 to 20, more preferably 4 to 10, and even more preferably 6 to 10.

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

The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. In addition, heteroaryl is monocyclic or condensed The ring is preferably a single ring or a condensed ring with a condensation number of 2 to 8, and more preferably a single ring or a condensed ring with 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 chromene ring. ring), xanthene ring, phenoxazine ring, pyrrole ring, pyrazole ring, isothiazole ring, isoxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indazine ring, isoindazine ring, indole ring, indazole ring, purine ring, quinazine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinazoline ring, oxoline Cinnoline ring, pteridine ring, carbazole ring, carboline ring, phenanthrine ring, acridine ring, perimidine ring, morpholine ring ( phenanthroline ring), phenarsazine ring, furazan ring and the like.

Examples of the substituent which the monovalent organic group may have include an alkyl group, a polymerizable group (for example, vinyl, (meth) acrylfluorenyl, epoxy, oxetanyl, etc.), a halogen atom, and a carboxyl group. , Carboxylic acid ester groups (for example, -CO ₂ CH ₃ and the like), hydroxyl groups, amido groups, halogenated alkyl groups (for example, fluoroalkyl groups, chloroalkyl groups), and the like. Moreover, as a substituent, the substituent which R <^1> in the said General formula (i) may have is also mentioned.

Examples of the divalent alkylene, alkylene, or heteroaryl group include: one hydrogen atom is removed from the linear, branched, or cyclic alkyl group, aryl group, or heteroaryl group; Derived bivalent linking group.

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

The copper phosphonate complex preferably has a structure represented by the following formula (F).

(In formula (F), R ³ and R ⁴ each independently represent a monovalent organic group. "*" Represents a site forming a coordination 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 copper phosphonate complexes are shown below.

[Chemical 25]

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

Substituted copper phosphinate complexes with copper as the central metal and acidified with substituted phosphinates The complex serves as a complex of the ligand. The substituted phosphinic acid compound that forms a ligand is preferably a compound represented by the following formula (G).

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

The compound represented by formula (G) and its salt 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 include the same groups as the monovalent organic groups described for R ³ and R ⁴ in the formula (E), and preferred ranges are also the same.

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

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

[Chemical 27]

(In formula (H), R ⁵ and R ⁶ each independently represent a monovalent organic group. "*" Represents a site forming a coordination 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 substituted copper phosphinate complex are shown below.

The phosphorus-containing copper complex is obtained by reacting a copper component with a phosphorus-containing compound (for example, phosphate, phosphonate, substituted phosphinic acid, etc.) or a salt thereof as a ligand.

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

The phosphorus-containing compound can be synthesized with reference to a known method, for example.

For example, a phosphate compound can be obtained by reacting 2-hydroxyethyl methacrylate, phenyl phosphate, and 1,3,5-triisopropylsulfonyl 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 mole ratio.

The reaction conditions when the copper component is reacted with the phosphorus-containing compound or a salt thereof are preferably set to, for example, a reaction at 20 ° C. to 50 ° C. for 0.5 hours or more.

It is preferable to have a maximum absorption wavelength of a copper-containing copper complex in a wavelength range of 700 nm to 1000 nm, more preferably a maximum absorption wavelength in a range of 720 nm to 890 nm, and still more preferably a maximum absorption range of 730 nm to 880 nm. Absorption wavelength. The maximum absorption wavelength can be measured using, for example, a Cary 5000 UV-Vis-NIR (spectrophotometer, manufactured by Agilent Technologies Co., Ltd.).

In addition, the phosphorus-containing copper complex is preferably having an absorbance of 0.04 or more (g / mL), more preferably 0.06 or more (g / mL), and even more preferably 0.08 or more (g / mL).

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

<<<< Copper sulfonate complex >>>>

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

(In formula (1), R ⁷ represents a monovalent organic group)

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

Specific examples of the monovalent organic group of R ⁷ in the general formula (I) include a hydrocarbon group, and specific examples include a linear, branched, or cyclic alkyl group, alkenyl group, and aryl group. These groups may be a divalent linking group (for example, linear or branched alkylene, cyclic cycloalkylene, arylene, -O-, -S-, -CO-,- COO-, -OCO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group).

The carbon numbers of the linear alkyl group, the branched alkyl group, the cyclic alkyl group, the alkenyl group, and the aryl group have the same meanings as those in the description of R ¹ in the general formula (i), and a preferable range The same.

The monovalent organic group may have a substituent, and examples of the substituent include a substituent that the monovalent organic group represented by R ³ and R ⁴ in the formula (E) may have. Examples of the substituent which the linear alkyl group and the branched alkyl group may have include at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. Examples of the substituent which the aryl group may have 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, and a sulfonic acid group is preferred. And at least one of a carboxylic acid group.

Examples of the divalent linking group include a linear or branched alkylene group, a cyclic alkylene group, and an arylene group, which are removed from the linear or branched or cyclic alkyl group and aryl group A divalent linking group derived from one hydrogen atom.

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

Examples of the substituent that R ⁷ may have when it is a linear alkyl group and a branched alkyl group include at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. Examples of the substituent that R ⁷ may have when it 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 formula (I) is preferably 80 to 750, more preferably 80 to 600, and even more preferably 80 to 450.

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

(In formula (J), R ⁸ represents a monovalent organic group. "*" Represents a site forming a coordination bond with copper)

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

Specific examples of the copper sulfonate complex are shown below.

[Chemical 31]

[Chemical 32]

[Chemical 33]

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

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

The sulfonic acid compound may be a commercially available sulfonic acid, or may 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 1: 1.5 to 1: 4 in terms of mole ratio. In this case, the sulfonic acid compound or a salt thereof may be one type, or two or more types may be used.

The reaction conditions when reacting a copper component with a sulfonic acid compound or a salt thereof are, for example, preferably at 20 ° C. to 50 ° C. for 0.5 hours or more.

Regarding the maximum absorption wavelength and the absorbance of the copper sulfonate complex, it has the same meaning as the phosphorus-containing copper complex, and the preferred range is also the same.

<< Other copper compounds >>

In addition to the above, a copper compound using a carboxylic acid as a ligand may be used as the copper compound used in the present invention. As the carboxylic acid, for example, a compound represented by the following formula (K) is preferred.

(In 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. For example, the monovalent organic group has the same meaning as the monovalent organic group R ⁷ in the general formula (I), and the preferable ranges thereof are also the same.

As specific examples of the carboxylic acid, for example, reference can be made to the description in paragraph 0029 of Japanese Patent Application Laid-Open No. 2013-253224 (corresponding to International Publication WO2013 / 168824 pamphlet 0029), and these contents are incorporated into the description of the present application. .

<<< Polymer Copper Compounds >>>>

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

The copper compound is, for example, a polymer copper complex containing a polymer containing an acid group ion site and a copper ion. The polymer copper complex has an acid-based ion site on the side chain of the polymer, and the acid-based ion site is bonded to copper (for example, to form a coordination bond), and a cross-linked structure is formed between the side chains using copper as a starting point. By using a polymer copper complex, heat resistance can be improved.

The copper component is preferably a compound containing divalent copper. The copper content in the copper component is preferably 2% by mass to 40% by mass, and more preferably 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, particularly preferred are copper hydroxide, copper acetate, and copper sulfate.

The acid group contained in the polymer containing an acid group or a salt thereof is not particularly limited as long as it is a group capable of reacting with the copper component, and is preferably a group that forms a coordination bond with the copper component. Specifically, an acid group having an acid dissociation constant (pKa) of 12 or less may be mentioned, and a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a phosphonium imino acid group, and the like are preferable. The polymer may have only one kind of acid group or two or more kinds of acid groups.

Examples of the atom or atomic group constituting the salt of the acid group include atomic groups such as a metal atom (especially an alkali metal atom) such as sodium, and tetrabutylammonium. In addition, in a 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 in at least 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 sulfonic acid. 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 Polymer Containing Acid Group or Its Salt >>>>>

A preferable example of the polymer containing an acid group or a salt thereof has a structure having a carbon-carbon bond in the main chain, and it is preferable to contain 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 an atomic group constituting a salt with a sulfonic acid group)

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

In 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-, -CO -, -COO-, -OCO-, -SO _2- , -NX- (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group containing a combination of these.

Examples of the divalent hydrocarbon group include a linear, branched, or cyclic alkylene or arylene. The hydrocarbon group may have a substituent, and is preferably unsubstituted.

The carbon number of the linear alkylene is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 6. The carbon number of the branched alkylene group is preferably 3 to 30, and more preferably 3 ~ 15, further preferably 3 ~ 6. The cyclic alkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and even more preferably 6 to 10.

The carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 14, even more preferably 6 to 10, and particularly preferably phenylene.

The heteroaryl group is not particularly limited, and a 5-membered ring or a 6-membered ring is preferred. In addition, the extended heteroaryl group may be a monocyclic ring or a condensed ring. A monocyclic ring or a condensed ring having a condensation number of 2 to 8 is preferred, and a monocyclic or condensed ring having a condensation number of 2 to 4 is more preferred.

In the formula (A1-1), the atom or atomic group constituting the salt with the sulfonic acid group represented by M ¹ has the same meaning as the atom or atomic group constituting the salt forming the acid group, and is preferably a hydrogen atom or an alkali metal atom.

As other constituent units other than the constituent unit represented by the formula (A1-1), reference can be made to paragraph number 0068 to paragraph number 0075 of Japanese Patent Laid-Open No. 2010-106268 (corresponding US Patent Application Publication No. 2011/0124824) [0112] to [0118]), the descriptions of the copolymerization components are incorporated into the description of this application.

Preferred other constituent units include constituent units represented by the following formula (A1-2).

[Chemical 36]

In the formula (A1-2), R ³ represents a hydrogen atom or a methyl group, and is 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 formula (A1-1). In particular, Y ^{2 is} preferably -COO-, -CO-, -NH-, a linear or branched alkylene group, a group containing a combination thereof, or a single bond.

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

When the polymer containing the structural unit represented by the formula (A1-1) contains other structural units (preferably, the structural unit represented by the formula (A1-2)), the structural unit represented by the formula (A1-1) and The Mohr of the structural unit represented by formula (A1-2) is more preferably 95: 5 to 20:80, and more preferably 90:10 to 40:60.

<<<<< Second Embodiment of Polymer Containing Acid Group or Its Salt >>>>>

As a polymer-type copper compound, a polymer having an acid group or a salt thereof and an aromatic hydrocarbon group and / or an aromatic heterocyclic group in the main chain (hereinafter referred to as an aromatic group-containing polymer), A polymer-type copper compound obtained by a 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. About an acid group or its salt, and a copper component, the copper obtained by the reaction of the said acid group or its salt containing polymer 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 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. Particularly preferred is phenyl, naphthyl or biphenyl. The aromatic hydrocarbon group may be monocyclic or polycyclic, and is preferably monocyclic.

The carbon number of the aromatic heterocyclic group is preferably 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 with a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. Examples of the hetero atom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom or an oxygen atom is preferred.

When the aromatic hydrocarbon group and the aromatic heterocyclic group have a substituent T, examples of the substituent T include 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), carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacrylic acid group, acrylic acid group, ether group, sulfonyl group, thioether group, fluorenyl group , Fluorenyl, hydroxy, carboxyl, aralkyl, etc., preferably an alkyl group (especially an alkyl group having 1 to 3 carbon atoms).

In particular, the polymer containing an aromatic group is preferably at least one polymer selected from the group consisting of a polyether fluorene polymer, a polyfluorene polymer, a polyether ketone polymer, a polyphenylene ether polymer, Polyimide-based polymer, polybenzimidazole-based polymer, polyphenylene-based polymer, phenol resin-based polymer, polycarbonate-based polymer, polyamide-based polymer, and polyester-based polymer. Examples of each polymer are shown below.

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

(Ph stands for phenylene, the same applies hereinafter)

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

Polyetherketone 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-)

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

Phenol resin polymer: a polymer having a main chain structure represented by (-Ph (OH) -CH _2- )

Polycarbonate 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-)

Polyether fluorene-based polymer, polyfluorene-based polymer, and polyetherketone-based polymer can be referred to, for example, those described in paragraph 0022 of Japanese Patent Laid-Open No. 2006-310068 and paragraph 0028 of Japanese Patent Laid-Open No. 2008-27890 The main chain structure incorporates these contents into the specification of this application.

For polyimide-based polymers, refer to the descriptions in paragraphs 0047 to 0058 of Japanese Patent Laid-Open No. 2002-367627 and Japanese Patent Laid-Open No. 2004-35891. The main chain structure described in the reported paragraphs 0018 to 0019 is incorporated into the description of this application.

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

(In 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 aromatic hydrocarbon group, and a preferable 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 other than -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 group containing a combination of these. 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 arylene group. The carbon number of the linear alkylene group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The carbon number of the branched alkylene group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6. The cyclic alkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and even more preferably 6 to 10. Regarding these linear, branched or cyclic alkylene groups, the hydrogen atom in the alkylene group may be substituted with a fluorine atom.

The case where the arylene group and the divalent linking group of the formula (A1-1) is an arylene group has the same meaning.

The aromatic heterocyclic group is not particularly limited, but is preferably a 5-membered ring or a 6-membered ring. In addition, the aromatic heterocyclic 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, and more preferably a monocyclic or condensed ring of a condensation number of 2 to 4.

In the formula (A1-3), the acid group or a salt thereof represented by X ¹ has the same meaning as the acid group or a salt thereof, and a preferable range is also the same.

The weight average molecular weight of the polymer containing a structural unit represented by Formula (A1-1), Formula (A1-2), or Formula (A1-3) is preferably 1,000 or more, more preferably 10 to 10 million, and even more preferably 30 to 1 million, especially good for 40 to 400,000.

Specific examples of the polymer containing the structural unit represented by the formula (A1-1), the formula (A1-2), or the formula (A1-3) include the compounds described below and salts of the following compounds. It is not limited to these compounds.

[Chemical 38]

<< Auxiliary near-infrared absorbing substance >>

The near-infrared absorbing composition of the present invention may further contain an auxiliary near-infrared absorbing substance different from the near-infrared absorbing substance in addition to the near-infrared absorbing substance. When the near-infrared absorbing composition of the present invention further contains an auxiliary near-infrared absorbing substance, it is possible to provide a composition having a more excellent light transmittance in the entire range of a wavelength of 450 to 550 nm when a film having a thickness of 300 μm or less is formed. . In addition, a near-infrared cut-off filter having a high light-shielding property (near-infrared shielding property) in the near-infrared range and a high light-transmittance (visible-light transmittance) in the visible light range can be provided.

The auxiliary near-infrared absorbing substance is preferably a metal oxide. The metal oxide is preferably a metal oxide having a maximum absorption wavelength in a wavelength range of 800 nm to 2000 nm. Examples include tungsten cesium oxide (CsWO _x ), quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), and zirconia (ZrO ₂ ). And metal oxides, such as spinel (MgAl ₂ O ₄ ), preferably tungsten cesium oxide.

The tungsten oxide-based compound is an infrared shielding material that has high absorption of infrared rays (especially light having a wavelength of about 800 nm to 1200 nm) (that is, high light shielding properties (shielding properties) against infrared rays) and low absorption of visible light. Therefore, by including the tungsten compound in the near-infrared absorbing composition of the present invention, it is possible to produce near-infrared cutoff with high light-shielding properties (infrared shielding properties) in the infrared range and high light-transmittance (visible light transmission properties) in the visible light range. filter.

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

M _x W _y O _z … (I)

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

0.001 ≦ x / y ≦ 1.1

2.2 ≦ z / y ≦ 3.0

Examples of the metal represented by M include alkali metals, alkaline earth metals, magnesium (Mg), Zirconium (Zr), chromium (Cr), manganese (Mn), iron (Fe), ruthenium (Ru), 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), thallium (Tl), Tin (Sn), lead (Pb), titanium (Ti), niobium (Nb), vanadium (V), molybdenum (Mo), tantalum (Ta), hafnium (Re), beryllium (Be), hafnium (Hf), Osmium (Os) and bismuth (Bi) are preferably alkali metals, more preferably Rb or Cs, and particularly preferably Cs. The metal of M may be one kind or two or more kinds.

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

When z / y is 2.2 or more, the chemical stability of the material can be further improved, and when z / y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, and the like, preferably CS _0.33 WO ₃ or Rb _0.33. WO ₃ and further preferably Cs _0.33 WO ₃ .

The metal oxide is preferably fine particles. The average particle diameter of the fine particles of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and even 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 due to light scattering, and the transmittance in the visible light range can be further improved. From the standpoint of avoiding light scattering, the smaller the average particle diameter of the metal oxide is, the better, 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, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by inert gas to the tungsten compound. Obtained by a method of heat treatment in a body environment or a reducing gas environment (see Japanese Patent No. 4096205).

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

The near-infrared absorbing composition of the present invention may also contain no auxiliary near-infrared absorbing substance. When the near-infrared absorbing substance is contained, the content of the auxiliary near-infrared absorbing substance is smaller than that of the total solid content of the near-infrared absorbing composition of the present invention. It is preferably 20% to 85% by mass, more preferably 30% to 80% by mass, and even more preferably 40% to 75% by mass.

The auxiliary near-infrared absorbing substance may be one kind, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably in the range.

<< hardening compound >>

The composition of the present invention may contain a curable compound. The curable compound may be a compound having a polymerizable group (hereinafter, sometimes referred to as a "polymerizable compound") or a non-polymerizable compound such as an adhesive. The sclerosing compound may be any of chemical forms such as a monomer, an oligomer, a prepolymer, and a polymer. As the hardening compound, for example, paragraphs 0070 to 0191 of Japanese Patent Laid-Open No. 2014-41318 (corresponding paragraphs 0071 to 0192 of International Publication WO2014 / 017669 pamphlet), and Japanese Patent Laid-Open No. 2014-32380 can be referred to. The descriptions of paragraphs 0045 to 0216 are incorporated into the description of the present application.

The curable compound is preferably a polymerizable compound. Examples thereof include compounds containing an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), and the like. As B The ethylenically unsaturated bond is preferably a vinyl group, a styryl group, a (meth) acrylfluorenyl group, or an allyl group.

Specific examples of the curable compound include a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate (preferably a trifunctional to 6 functional (meth) acrylate), and a polyacid Modified acrylic oligomer, epoxy resin, polyfunctional epoxy resin, etc.

The curable compound may be monofunctional or polyfunctional, and is preferably polyfunctional. By containing a polyfunctional compound, near-infrared shielding properties and heat resistance can be further improved. The number of functional groups is not particularly limited, but is preferably difunctional to 8 functional, and more preferably trifunctional to 6 functional.

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

The sclerosing compound may be only one kind, or two or more kinds. When it is two or more types, it is preferable that the total amount falls within the above range.

<<< Compounds containing ethylenic unsaturated bonds >>>

As an example of a compound containing an ethylenically unsaturated bond, the descriptions in paragraphs 0033 to 0034 of Japanese Patent Laid-Open No. 2013-253224 can be referred to, and the contents are incorporated into this specification.

As the compound containing an ethylenically unsaturated bond, ethoxylated modified pentaerythritol tetraacrylate (commercially available NK Ester) ATM-35E; Xinzhong Village Chemical Co., Ltd.), dipentaerythritol triacrylate (KAYARAD D-330, commercially available; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available, Kayarad) (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available product is Kayarad D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (commercially available is KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd .; A-DPH-12E, manufactured by Shin Nakamura Chemical Co., Ltd.), and these (A The structure of acryl fluorenyl group interposed between ethylene glycol residues and propylene glycol residues. In addition, these oligo type may be used.

In addition, the description of the polymerizable compound in paragraphs 0034 to 0038 of Japanese Patent Laid-Open No. 2013-253224 can be referred to and incorporated into the present specification.

In addition, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2012-208494 paragraph 0477 (corresponding to US Patent Application Publication No. 2012/0235099 [0585]) and the like are incorporated into this application. Case description.

In addition, diglycerin oxide (EO) modified (meth) acrylate (commercial product M-460; manufactured by Toa Synthetic) 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. Examples include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

The compound containing an ethylenically unsaturated bond may be a polyfunctional monomer, and may also be It has acid groups such as a carboxyl group, a sulfonic acid group, and a phosphate group. As long as the compound containing an ethylenically unsaturated bond has an unreacted carboxyl group as in the case of the mixture described above, it can be used directly, and a non-aromatic carboxylic anhydride can be reacted with the hydroxyl group of the ethylenic compound and introduced if necessary. Acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexa Hydrophthalic anhydride, succinic anhydride, maleic anhydride.

The compound having an acidic ethylenic unsaturated bond having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has an acid by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The polyfunctional monomer of the group is particularly preferably an ester of which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, Aronix series M-305, M-510, M-520, etc., which are polyacid-modified acrylic oligomers manufactured by Toa Synthesis Co., Ltd.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mg-KOH / g to 40 mg-KOH / g, and particularly preferably 5 mg-KOH / g to 30 mg-KOH / g. When two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid value of the entire polyfunctional monomer is adjusted within the above range.

<<< 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 monomer or oligomer having two or more epoxy groups in a molecule. Examples include: bisphenol A epoxy resin, bisphenol F epoxy resin, Phenol novolac epoxy resin, cresol novolac epoxy resin, aliphatic epoxy resin, etc. In addition, a monofunctional or polyfunctional glycidyl ether compound is also mentioned, and a polyfunctional aliphatic glycidyl ether compound is preferable.

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

These compounds can be a commercially available product or can be obtained by introducing an epoxy group into the side chain of the polymer.

As a commercially available product, for example, reference can be made to the description of paragraph 0191 of Japanese Patent Laid-Open No. 2012-155288 and the like, and these contents are incorporated into the specification of the present application.

Examples of commercially available products include: Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, and Denacol EX Polyfunctional glycidyl ether compounds such as -321L and Denacol EX-850L (the above are 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 be used in the same manner.

In addition, you can also mention: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN) EP-4011S (the above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (the above is the ADEKA), JER1031S, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (the above are manufactured by Daicel Chemical Industry Co., Ltd.), Cyclomer P ACA 200M, Cyclomer P ACA 230AA, Sacma (Cyclomer) P ACA Z250, Cyclomer P ACA Z251, Cyclomer P ACA Z300, Cyclomer P ACA Z320 (The above are manufactured by Daicel Chemical Industry Co., Ltd.) )Wait.

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

In addition, 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 a molecule, aronoxetine may be used. Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by Toa Kosei 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 also be used. Saturated compounds. Such compounds can be referred to, for example, the description in paragraph 0045 of Japanese Patent Application Laid-Open No. 2009-265518, and the contents are incorporated into the specification of the present application.

The compound containing an epoxy group or an oxetanyl group may also contain a polymer having an epoxy group or an oxetanyl group as a repeating unit. Specific examples include the following: Polymers (copolymers) of multiple units.

<<< Other hardening compounds >>>

Moreover, as a curable compound, it is preferable to contain the polyfunctional monomer which has a caprolactone modified structure.

As a polyfunctional single body having a caprolactone modified structure, reference may be made to the descriptions of paragraphs 0041 to 0045 of Japanese Patent Laid-Open No. 2013-253224, and the contents are incorporated into the present specification.

Such a polyfunctional singlet having a caprolactone modified structure is marketed, for example, as a KAYARAD DPCA series by Nippon Kayaku Co., Ltd., and examples include DPCA-20 (Japanese Patent Laid-Open) 2014-041318 Paragraph 0083 to Paragraph 0085 in formulas (1) to (0) m = 1, the number of groups represented by formula (2) = 2, compounds in which all of R ¹ are hydrogen atoms), DPCA-30 (a compound in which m = 1 in the formulae (1) to (3), the number of groups represented by the formula (2) = 3, and all of R ¹ is a hydrogen atom), DPCA-60 (the compound In the formulae (1) to (3), m = 1, the number of groups represented by the formula (2) = 6, and compounds in which all of R ¹ is a hydrogen atom), DPCA-120 (the formulas (1) to (1)) (3) m = 2, the number of groups represented by the formula (2) = 6, a compound in which all of R ¹ is a hydrogen atom), and the like.

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

Examples of commercially available products include tetrafunctional acrylate SR-494 with 4 ethoxylated chains manufactured by Sartomer Corporation, and 6 with pentyloxy chains manufactured by Nippon Kayaku Co., Ltd. Hexafunctional acrylate DPCA-60, trifunctional acrylate TPA-330 with 3 isobutoxy chains, etc.

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

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

In formula (30), R ¹ represents a hydrogen atom or an organic group. Examples of the organic group include 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 these groups and a divalent linking group Combined base.

Specific examples of such an organic group are preferably -OR ', -SR', or a cyclic group containing these groups and-(CH ₂ ) _m- (m is an integer of 1 to 10) and 5 to 10 carbon atoms. A combination of at least one of alkylene, -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) , Branched or cyclic alkyl groups having 3 to 7 carbon atoms), aryl groups having 6 to 10 carbon atoms, or a combination containing an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms base.

In the formula (30), R ¹ and C may be bonded to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is a nitrogen atom in the formula (30). The heterocyclic structure is preferably a 5-membered ring or 6-membered ring structure, and more preferably a 5-membered ring structure. The heterocyclic structure may also be a condensed ring, preferably a monocyclic ring.

Specific examples of particularly preferred R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, -OR '(R' is a linear alkyl group having 1 to 5 carbon atoms), and-(CH ₂ ) _m- (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), a combination of R ¹ and C in the formula (30) to form a heterocyclic structure (preferably Is a 5-membered ring structure).

The compound having a partial structure represented by the formula (30) is preferably represented by (main structure of a polymer-partial structure of the formula (30)-R ¹ ), or by (A-the formula (30) is represented by a partial 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. In addition, B is a group containing-(CH ₂ ) _m- (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), and a combination of a partial structure of the formula (30) and a polymerizable group .

Examples of the compound having a partial structure represented by the formula (30) include a structure represented by any one of the following formulae (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 represents a hydrogen atom or an organic group. In the formula (1-5), L ⁴ represents a divalent linking group, and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or an organic group)

In the formula (1-1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. The organic group has the same meaning as R ¹ in the formula (30), and a preferable 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 is preferably-(CH _{2) m-} (m is an integer of 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, and -O-, -CO-, -COO- and A group of at least one combination of -NH- is more preferably-(CH ₂ ) _m- (m is an integer of 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 may also be substituted. The alkyl group may be any of linear, branched, and cyclic groups, 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 even more preferably an alkyl group having 1 to 6 carbon atoms.

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

Examples of the substituent include a polymerizable group, a halogen atom, an alkyl group, a carboxylic acid ester group, a halogenated alkyl group, an alkoxy group, a methacrylic acid group, an acrylic acid group, an ether group, a sulfonyl group, and a thioether. Groups, fluorenyl groups, fluorenyl groups, hydroxyl groups, carboxyl groups, and the like. Among these substituents, a polymerizable group (for example, vinyl, (meth) acrylfluorenyl, (meth) acrylfluorenyl, epoxy, aziridinyl, etc.) is preferred, and vinyl is more preferred .

The compound having a partial structure represented by the formula (30) may be a monomer or a polymer, and is preferably a polymer. That is, the compound having a partial structure represented by the formula (30) is preferably a compound represented by the formula (1-1) or the formula (1-2).

When the compound having a partial structure represented by the formula (30) is a polymer, it is preferable that the side chain of the polymer contains the partial structure.

The molecular weight of the compound having a partial structure represented by the formula (30) is preferably 50 to 1,000,000, and more preferably 500 to 500,000. By setting to this molecule The amount can achieve the effect of the invention more effectively.

Specific examples of the compound having a partial structure represented by the formula (30) include a compound having the following structure or the following exemplary compounds, but are not limited to these compounds. In the present invention, it is particularly preferred that the compound having a partial structure represented by the formula (30) is polyacrylamide.

Specific examples of the compound having a partial structure represented by the formula (30) include a water-soluble polymer, and preferred main chain structures include polyvinylpyrrolidone and poly (methyl). ) Acrylamide, polyamine, polyurethane, polyurea. The water-soluble polymer may be a copolymer, and the copolymer may be a random copolymer. The water-soluble polymer is preferably a water-soluble polyamine resin.

As the polyvinyl pyrrolidone, trade names K-30, K-85, K-90, K-30W, K-85W, and K-90W (manufactured by Nippon Catalytic Corporation) can be used.

Examples of poly (meth) acrylamide include polymers and copolymers of (meth) acrylamide. Specific examples of acrylamide include acrylamide, N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylamine Acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (aminesulfonylphenyl) Acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-benzene Acrylamide, N-hydroxyethyl-N-methacrylamide, and the like. Moreover, methacrylamide corresponding to these compounds can also be used similarly.

Examples of the water-soluble polyamide resin include compounds obtained by copolymerizing a polyamide resin and a hydrophilic compound. The so-called water-soluble polyamine resin derivative refers to, for example, a water-soluble polyamine resin as a raw material, and a hydrogen atom of a amine bond (-CONH-) via a methoxymethyl group (-CH ₂ OCH ₃ ). Like a substituted compound, a compound in which the structure of the amidine bond is changed by replacing or performing an addition reaction on the atoms in the molecule of the water-soluble polyamidine resin.

Examples of the polyamidoamine resin include so-called "n-nylon" synthesized by polymerization of an omega amino acid and so-called "n, m-nylon" synthesized by copolymerization of a diamine and a dicarboxylic acid. Among these, from the viewpoint of imparting hydrophilicity, a copolymer of a diamine and a dicarboxylic acid is preferable, and a reaction product of ε-caprolactam and a dicarboxylic acid is more preferable.

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

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 aminoethylpiperazine and bisaminopropyl Piperazine, α-dimethylamino-ε-caprolactam and the like.

On the other hand, in a compound obtained by copolymerizing a polyamide resin and a hydrophilic compound, the main chain of the polyamide resin is copolymerized, for example, from a group consisting of a hydrophilic nitrogen-containing cyclic compound and a polyalkylene diene. At least one of the groups consisting of alcohols has a hydrogen bonding capability of the amido bond of the polyamide resin that is greater than that of N-methoxymethylated nylon.

Among compounds obtained by copolymerizing a polyamide resin and a hydrophilic compound, 1) ε-caprolactam and a hydrophilic nitrogen-containing cyclic compound and a dicarboxylic acid, and 2) ε- Reaction product of caprolactam with polyalkylene glycol and dicarboxylic acid.

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

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

<< Polymerization initiator >>

The near-infrared absorbing composition of the present invention may contain a polymerization initiator. The content of the polymerization initiator is preferably 0.01% by mass to 30% by mass, and more preferably 0.1% by mass to 20%. Mass%, particularly good, 0.1 mass% to 15 mass%. The polymerization initiator may be only 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 a polymerizable compound by either light or heat, or both, and can be appropriately selected according to the purpose.

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

When the polymerization of the polymerizable compound is initiated by heat, a thermal polymerization initiator is preferred. The thermal polymerization initiator is preferably one which decomposes at 150 ° C to 250 ° C.

The polymerization initiator is preferably a compound having at least an aromatic group, and examples thereof include a fluorenyl phosphine compound, an acetophenone compound, an α-amino ketone compound, a benzophenone compound, and a benzoin ether compound. Ketal derivative compounds, thia anthrone compounds, oxime compounds, hexaaryl biimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, hydrazone compounds, hydrazone compounds, Onium salt compounds such as azineium compounds and metallocene compounds, organic boron salt compounds, difluorene compounds, thiol compounds, and the like.

As the polymerization initiator, reference can be made to the paragraphs 0218 to 0251 of Japanese Patent Laid-Open Publication No. 2014-41318 (corresponding to paragraphs 0220 to 0253 of the pamphlet of International Publication WO2014 / 017669), and the contents are incorporated herein. Application specification.

As the oxime compound, IRGACURE-OXE01 (manufactured by BASF), Yilujia, which are commercially available products, can be used. (IRGACURE) -OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka arc Luz NCI-831 (manufactured by ADEKA) , Adeka arc Luz NCI-930 (manufactured by Adeco).

As the acetophenone-based initiator, commercially available products such as IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, all of which are BASF Japan) can be used. (BASF Japan).

As the fluorenylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF Japan) can be used.

The present invention may also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include a compound described in Japanese Patent Laid-Open No. 2010-262028, a compound 24, Compound 36 to Compound 40 described in Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent Laid-Open Compound (C-3) and the like described in Gazette 2013-164471. This content is incorporated into this manual.

<< Alkali soluble resin >>

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

The alkali-soluble resin is a linear organic polymer, and it may be appropriately contained in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkali-soluble resin is selected from at least one group which promotes alkali-solubility. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferred from the viewpoint of development control Specifically, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. As the alkali-soluble resin, reference may be made to the following paragraphs in Japanese Patent Application Laid-Open No. 2012-208494 to paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of the specification of U.S. Patent Application Publication 2012/0235099). Codified in the specification of this application.

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

In addition, when the pattern is formed by alkali development without using the near-infrared absorbing composition of the present invention, it is of course possible to adopt a form not containing an alkali-soluble resin.

<< Interactive Agent >>

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

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

Particularly preferred is that the near-infrared absorbing composition of the present invention contains at least one of a fluorine-based surfactant and a silicone-based surfactant. Thereby, the solution characteristics (especially fluidity) when the coating liquid is prepared are further improved, and the uniformity or liquid saving of the coating thickness is further improved.

That is, the near-infrared absorbing composition contains at least one of a fluorine-based surfactant and a silicone-based surfactant, thereby reducing the interfacial tension between the surface to be coated and the coating liquid, and dampening the surface to be coated. The coating property is improved, and the coating property of the coating liquid to the surface to be coated is improved. Therefore, even when a thin film of about several micrometers (μm) is formed with a small amount of liquid, film formation with a uniform thickness with small thickness unevenness can be performed more preferably.

The fluorine content in the fluorine-based surfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and even more preferably 7% to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film or the liquid saving property, and also has good solubility in the near-infrared absorbing composition.

Specific examples of the fluorine-based surfactant include those described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-41318 (paragraphs 0060 to 0064 of the corresponding International Publication WO2014 / 17669 pamphlet) and the like. These contents are incorporated into the specification of this application.

Examples of commercially available products of fluorine-based surfactants include: (Megafac) F-171, Megafac F-172, Megafac F-173, Megafac F-176, Megafac F-177, Megafac F- 141, Megafac F-142, Megafac F-143, 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 (Manufactured by DIC), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above are manufactured by Sumitomo 3M), and Shafron ( Surflon) S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Shaflon ( Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (The above are manufactured by Asahi Glass Co., Ltd.) Wait.

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

[Chemical 43]

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

Examples of the non-ionic surfactant include polyoxyethyl ether, polyoxyethyl allyl ether, polyoxyethyl fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene fatty acid ester. Oxyethylene ethyl sorbitan fatty acid ester, polyoxyethyl alkylamine, glycerol fatty acid ester, oxyethyl oxyethylene propylene block copolymer, acetylene glycol surfactant, acetylene Polyoxyethylene oxide, etc. These nonionic surfactants can be used alone or in combination of two or more.

Specific product names can be enumerated: Sofino (Surfinol 61), Sofino (Surfinol 82), Sofino (Surfinol 104), Sofino (Surfinol 104E), Sofino (Surfinol 104H), Sofino (surfynol) 104A, surfynol 104BC, surfynol 104DPM, surfynol 104PA, surfynol 104PG-50, surfynol 104S, and sofino (surfynol) 420, sofino (surfynol) 440, sofino (surfynol) 465, sofino (surfynol) 485, sofino (surfynol) 504, sofino (surfynol) CT-111, sofino (surfynol) CT-121, surfynol CT-131, surfynol CT-136, surfynol CT-141, suffino (surfynol) CT-151, surfynol CT-171, surfynol CT-324, surfynol DF-37, surfynol DF-58, suffino (surfynol) DF-75, 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 Chemical Co., Ltd. and Air Products & Chemicals), Olfine A, Olfine ) B, Olfine AK-02, Olfine CT-151W, Olfine E1004, Olfine E1010, Olfine P, Olfine (Olfine) SPC, Olfine STG, Olfine Y, Olfine 32W, Olfine PD-001, Olfine PD-002W, Austria Olfine PD-003, Olfine PD-004, Olfine EXP.4001, Olfine EXP.4036, Olfine EXP.4051, Austria Olfine AF-103, Olfine AF-104, Olfine SK-14, Olfine AE-3 (the above is Nissin Chemical Co., Ltd.), Azerbaijan Acetylenol E00, Acetylenol E13T, Acetylenol E40, Acetylenol E60, Acetylenol E81, Acetylenol ) E100, Acetylenol E200 (all above are trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.), etc. Among these, Olfine E1010 is preferred.

In addition, as the non-ionic surfactant, specific examples include non-ionic surfactants described in Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0553 (corresponding US Patent Application Publication No. 2012/0235099, [0679]) and the like. Ionic surfactants are incorporated into this specification.

Specific examples of the cationic surfactant include the cationic surfactant described in Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0554 (corresponding to US Patent Application Publication No. 2012/0235099 [0680]). These contents are incorporated into the specification of this application.

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

Examples of the silicone-based surfactants include the silicone-based surfactants described in Japanese Patent Application Publication No. 2012-208494, paragraph 0556 (corresponding to US Patent Application Publication No. 2012/0235099, [0682]), and the like. These contents are incorporated into the specification of this application. In addition, you can also exemplify: Toray. `` Toray Silicone SF8410 '', `` Toray Silicone SF8427 '', `` Toray Silicone SH8400 '', `` Toray Silicone '' (manufactured by Toray-Dow corning) Toray Silicone ST80PA "," Toray Silicone ST83PA "," Toray Silicone ST86PA "," TSF-400 "manufactured by Momentive Performance Materials "," TSF-401 "," TSF-410 "," TSF-4446 "," KP321 "," KP323 "," KP324 "," KP340 ", etc. manufactured by Shin-Etsu Silicone Co., Ltd.

<< Solvent >>

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

As the organic solvent, for example, alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethylmethane, Cyclops and others. These may be used alone or in combination of two or more. When two or more solvents are used in combination, a mixed solution composed of two or more solvents selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl Cellosolve 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 alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph 0136 of Japanese Patent Application Laid-Open No. 2012-194534, and the contents are incorporated into the description of the present application.

Specific examples of the esters, ketones, and ethers include those described in paragraph 0497 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding US Patent Application Publication No. 2012/0235099 [0609]). Further examples include n-pentyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, and ethylene glycol monobutyl ether ethyl. Esters and so on.

As the solvent, it is preferred to use at least one or more selected from the group consisting of a ring Hexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate, and propylene glycol monomethyl ether.

The content of the solvent in the near-infrared absorbing composition of the present invention is preferably such that the total solid content of the near-infrared absorbing composition of the present invention becomes 5 to 90% by mass, and more preferably 10 to 80% by mass. The amount is preferably 20% 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 hardening compound during the production or storage of the composition.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, third-butylcatechol, benzoquinone, 4,4'- Thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), N-nitrosophenylhydroxyl Cerium amine salts and the like are 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 0.01% to 5% by mass relative to the total solid content of the near-infrared absorbing composition of the present invention.

<< Other ingredients >>

As long as the near-infrared absorbing composition of the present invention does not impair the effect of the present invention, other components may be appropriately selected and used according to the purpose.

Examples of other components that can be used in combination include a dispersant, a sensitizer, a cross-linking agent (a cross-linker aqueous solution), acetic anhydride, a silane compound, a hardening accelerator, a filler, Thermal polymerization inhibitors, plasticizers, etc., and can also be used in combination with adhesion promoters on the surface of the substrate and other additives (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promotion). Agents, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.).

For these components, refer to, for example, paragraph number 0183 to paragraph number 0228 of Japanese Patent Laid-Open No. 2012-003225 (corresponding to [0237] to [0309] of the specification of US Patent Application Publication No. 2013/0034812), Japanese Patent Laid-Open Paragraph number 0101 to paragraph number 0102 of 2008-250074, paragraph number 0103 to paragraph number 0104 of Japanese Patent Laid-Open No. 2008-250074, paragraph number 0107 to paragraph number 0109 of Japanese Patent Laid-Open No. 2008-250074, The descriptions of paragraph number 0159 to paragraph number 0184 in Japanese Patent Laid-Open No. 2013-195480 are incorporated in the description of the present application.

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

<Preparation and use of near-infrared absorbing composition>

Since the near-infrared absorbing composition of the present invention can be made into a liquid state, for example, by applying the near-infrared absorbing composition of the present invention to a substrate or the like and drying it, the near-infrared cut filter can be easily manufactured.

For the purpose of removing foreign matter or reducing defects, it is preferable to filter the infrared absorbing composition with a filter. The filter can be used without particular limitation as long as it has been used for filtering purposes and the like. Examples include fluororesins such as polytetrafluoroethylene (PTFE), polyfluorene such as nylon-6, and nylon-6,6. Filters for polyolefin resins (including those with high density and ultra-high molecular weight) such as amine resins, polyethylene, and polypropylene (Poly Propylene, PP). Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 2.5 μm, and still more preferably 0.01 μm to 1.5 μm. By setting the pore diameter of the filter to the above range, fine foreign matter can be reliably removed.

When using filters, different filters can also be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, the pore diameter after the second filtration is preferably larger than the pore diameter of the first filtration. In addition, the first filters having different pore diameters in the above range may be combined. The pore size here can refer to the nominal value of the filter maker. Commercially available filters can be obtained, for example, from Japan Pall Corporation, Advantec Toyo Corporation, Entegris Corporation (formerly Mykrolis, Japan) ) Co., Ltd.) or Kitaza Micro Filter Co., Ltd.

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

For example, after filtering by the first filter, other components may be added and filtered. Line 2 is filtered.

Regarding the viscosity of the infrared absorbing composition, for example, when the infrared absorbing layer is formed by coating, it is preferably at 1 mPa. s ~ 3000mPa. The range of s. The lower limit is preferably 10 mPa. above s, more preferably 100mPa. s or more. The upper limit is preferably 2000 mPa. Below s, more preferably 1500mPa. s or less.

When the near-infrared 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 further preferably 100mPa. s ~ 1500mPa. s.

When the near-infrared absorbing composition of the present invention is a near-infrared cut-off filter used on the light-receiving side of a solid-state imaging element, and the near-infrared cut-off filter is formed by coating, from the viewpoints of thick film formation and uniform coating properties In particular, it is preferably 10 mPa. s ~ 3000mPa. s, more preferably 500mPa. s ~ 1500mPa. s, and further preferably 700 mPa. s ~ 1400mPa. s.

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

The use of the near-infrared absorbing composition of the present invention is not particularly limited, and it can be preferably used for forming a near-infrared cut filter and the like. For example, it can be preferably used for a near-infrared cut-off filter on the light-receiving side of a solid-state imaging element (for example, a near-infrared cut-off filter for a wafer level lens, etc.), and on the back side of a solid-state imaging element (and The light-receiving side is the opposite side). Particularly suitable as near-infrared cut filter for the light-receiving side of a solid-state imaging element Device.

<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 curing the near-infrared absorbing composition of the present invention.

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

In the near-infrared cut filter of the present invention, it is preferable that the light transmittance satisfies at least one of the following conditions (1) to (10), and it is particularly preferable that all conditions are satisfied.

(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more 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, still more 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, still more 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, still more 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, still more 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, and more preferably 15% Below, it is more 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, still more 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, still more 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, still more 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, still more 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 appropriately selected according to the purpose, and is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less. The lower limit of the film thickness of the near-infrared cut filter of the present invention is not particularly limited. For example, it is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more.

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

The near-infrared cut filter of the present invention has a light transmittance at a wavelength of 680 nm of 10% or less, and 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 20% or less in a range of at least one wavelength of 700 nm to 1100 nm, and further preferably in the entire range of 700 nm to 1100 nm. Transmittance 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 10% or less at at least one wavelength in the range of 800 nm to 900 nm, and more preferably the entire range of the wavelength 800 nm to 900 nm. The internal light transmittance is 10% or less.

According to the present invention, a wide range of visible light with high transmittance can be ensured, and a near-infrared cut filter having high near-infrared shielding properties can be provided.

The near-infrared cut filter of the present invention can be used to have absorption. Lenses that cut off near-infrared functions (optical lenses for cameras such as digital cameras, mobile phones, and car cameras, optical lenses such as f-θ lenses, pick-up lenses), optical filters for semiconductor light-receiving elements, Near-infrared absorbing filter or near-infrared absorbing plate for energy-saving blocking of heat rays, agricultural coating agent for selectively using sunlight, recording medium using near-infrared absorbing heat, electronic equipment, or photo Near-infrared filters, safety goggles, sunglasses, hot-line blocking film, optical text reading records, anti-copying of confidential documents, photoreceptors for electronic photos, laser welding, etc. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Manufacturing method of near-infrared cut filter>

The near-infrared cut filter of the present invention can be manufactured by the following steps: forming a film by applying (preferably, a dropping method, coating or printing) the near-infrared absorbing composition of the present invention to a support; dry. The film thickness, the laminated structure, and the like can be appropriately selected according to the purpose. In addition, a step of forming a pattern may be further performed.

The step of forming a film can be performed by using a method such as drop casting (drop cast), spin coater, slit spin coater, slit coater, screen printing, applicator coating, and the like. The infrared absorbing composition is applied to a support and implemented. In the case of the dropping method (drop casting), it is preferable to form a dropping region of a near-infrared absorbing composition using a photoresist as a partition wall with a predetermined film thickness so that a uniform film can be obtained. Regarding the film thickness, the amount of the composition to be added, the solid content concentration, and the area of the area to be added can be adjusted. The thickness of the film after drying is not particularly limited, and can be appropriately selected according to the purpose. The thickness of the film is, for example, preferably 1 μm to 500 μm, more preferably 1 μm to 300 μm, and particularly preferably 1 μm to 200 μm. In the present invention, even when such a film is used, the near-infrared light-shielding property can be maintained.

The support may be a transparent substrate including glass or the like. It may also be a solid-state imaging device. Alternatively, it may be another substrate provided on the light-receiving side of the solid-state imaging element. Alternatively, it may be a layer such as a planarization layer provided on the light-receiving side of the solid-state imaging element.

In the step of drying the film, the drying conditions also differ depending on the components, the type of solvent, the usage ratio, etc., and it is performed at a temperature of 60 ° C to 150 ° C for about 30 seconds to 15 minutes.

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

The manufacturing method of the near-infrared cut filter may include other steps. The other steps are not particularly limited, and can be appropriately selected according to 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 cited.

<< Before heating step. Post-heating steps >>

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

<< Hardening step >>

The hardening treatment step is a step of hardening the formed film as necessary. 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 according to the purpose, and examples thereof include a whole surface exposure treatment and a whole surface heating treatment. Herein, the "exposure" used in the present invention is used in the sense that it includes not only light of various wavelengths but also radiation such as electron beams and X-rays.

The exposure is preferably performed by irradiation with radiation. In particular, as the radiation that can be used during exposure, ultraviolet rays or visible light such as electron beams, KrF, ArF, g-rays, h-rays, and i-rays are preferably used.

Examples of the exposure method include stepper exposure or 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 .

As a method of the whole surface exposure process, the method of exposing the whole surface of the said film formed is mentioned, for example. When the near-infrared absorbing composition contains a polymerizable compound, By the entire surface exposure, the hardening of the polymerized component in the film formed of the composition is promoted, the hardening of the film is further advanced, and the mechanical strength and durability are improved.

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

In addition, a method of heating the entire surface includes a method of heating the entire surface of the formed film. By heating the entire surface, the film strength of the pattern can be increased.

The heating temperature of the entire surface heating is preferably 120 ° C to 250 ° C, and more preferably 160 ° C to 220 ° C. When the heating temperature is 120 ° C or higher, the film strength is increased by heat treatment. When the heating temperature is 250 ° C or lower, the components in the film can be prevented from decomposing and the film quality becomes weak and brittle.

The heating time of the whole surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.

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

<Camera Module, Manufacturing Method of Camera Module>

A camera module of the present invention includes a solid-state imaging element and a near-infrared cut-off filter disposed on a light-receiving side of the solid-state imaging element.

In addition, the camera module manufacturing method of the present invention manufactures a camera module having a solid-state imaging element and a near-infrared cut-off filter disposed on a light-receiving side of the solid-state imaging element, and the method of manufacturing the camera module includes the following steps: The near-infrared absorbing composition of the present invention is applied by the light-receiving side of the solid-state imaging element. A film is formed.

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

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

In the camera module 10, incident light hν from the outside sequentially passes 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 element 11.

The solid-state imaging element 11 includes, for example, an imaging element 16, an interlayer insulating film (not shown), a matrix layer (not shown), a color filter 17, and an overcoat layer (not shown) in this order on the main surface of a silicon substrate as a base. ) 、 微镜 18。 Micro lens 18. The color filters 17 (the red color filter, the green color filter, and the blue color filter) or the microlenses 18 are respectively arranged so as to correspond to the imaging element 16.

In addition, it is also possible to use a form in which the near-infrared cut-off filter 13 is provided instead of the surface of the flattening layer 12, and the surface of the microlens 18, between the matrix layer and the color filter 17, or the color filter 17 and the outer coating Between layers, a near-infrared cut filter 13 is provided. For example, the near-infrared cut-off filter 13 may be provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. If set at this position, the steps of forming a near-infrared cut-off filter can be simplified, and unnecessary near-infrared rays to the microlenses can be cut off sufficiently, so the near-infrared blocking property can be further improved.

The near-infrared cut filter of the present invention can be used in a reflow soldering step. By manufacturing a camera module using a reflow process, automatic mounting of electronic component mounting substrates and the like that must be soldered can be achieved, and productivity can be improved significantly compared to a case where a reflow process is not used. Furthermore, since it can be performed automatically, cost reduction can also be achieved. When it is used in the reflow step, it is exposed to a temperature of about 250 ° C to 270 ° C. Therefore, the near-infrared cut filter is preferably heat resistant that can withstand the reflow step (hereinafter also referred to as "reflow resistance"). ").

In the present specification, "having reflow resistance" refers to a characteristic of being maintained as a near-infrared cut filter before and after heating at 200 ° C for 10 minutes. It is more preferable to maintain the characteristics before and after heating at 230 ° C for 10 minutes. Furthermore, it is preferable to maintain the characteristics before and after heating at 250 ° C for 3 minutes. When it does not have reflow resistance, the infrared absorption ability of the near-infrared cut-off filter may be reduced or the function as a film may become insufficient when held under the conditions.

The present invention also relates to a method for manufacturing a camera module including a step of performing a reflow process. The near-infrared cut-off filter of the present invention maintains near-infrared absorbing ability even if it has a reflow soldering step, so it will not damage the small size and light weight. Features of high-performance camera modules.

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

As shown in FIG. 2, the camera module has a solid-state imaging element 11, a planarization layer 12, and ultraviolet rays in this order. The infrared light reflection film 19, the transparent base material 20, the near-infrared absorbing layer (near-infrared cut filter) 21, and the anti-reflection layer 22.

UV. The infrared light reflecting film 19 has an effect of imparting or improving a function of a near-infrared cut-off filter. For example, reference may be made to paragraphs 0033 to 0039 of Japanese Patent Application Laid-Open No. 2013-68688, and the contents are incorporated into the specification of the present application.

The transparent substrate 20 transmits light with a wavelength in the visible light range. For example, reference may be made to paragraphs 0026 to 0032 in Japanese Patent Application Laid-Open No. 2013-68688, and the contents are incorporated into the description of the present application.

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

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

As shown in FIG. 3, the camera module may also have a solid-state imaging element 11, a near-infrared absorbing layer (near-infrared cut filter) 21, an anti-reflection layer 22, a flattening layer 12, an anti-reflection layer 22, and a transparent substrate in this order. 20 and UV. Infrared light reflecting film 19.

As shown in FIG. 4, the camera module can also have a solid-state imaging element 11, a near-infrared absorbing layer (near-infrared cut filter) 21, and ultraviolet rays in this order. The infrared light reflection film 19, the planarization layer 12, the anti-reflection layer 22, the transparent substrate 20 and the anti-reflection layer 22.

<Compound>

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

The compound of the present invention is a compound represented by the general formula (1) described in the near-infrared absorbing substance of the near-infrared absorbing composition of the present invention. The ranges are the same.

Although the detailed reason is not clear, since the group represented by R ¹ of the compound of the present invention contains a halogen atom, heat resistance and light resistance can be improved. In addition, the transmittance in the wavelength range of 650 nm to 750 nm can be further reduced. In particular, by including a fluorine atom as a halogen atom, heat resistance can be further improved. The nucleophilicity of adjacent anions is reduced by the electron-drawing action of fluorine atom (in other words, the stability of anions is increased). Therefore, it is considered that it is difficult to decompose the compound represented by the general formula (1) due to anions when heating, and it is heat resistant Sexual improvement. Furthermore, it is considered that the larger the number of fluorine atoms, the lower the nucleophilicity of the anion, and therefore the higher the heat resistance.

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

The compound of the present invention can be preferably used, for example, in the formation of a near-infrared cut filter 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 plasma display panels (PDP) or solid-state imaging elements such as CCDs, optical filters in hot-line shielding filters, write-once optical discs (CD-R), or Light-to-heat conversion material in flash-melt fixing material. In addition, it can also be used as information display material in security ink or invisible barcode ink.

<Photosensitive resin composition>

Next, the photosensitive resin composition of this invention is demonstrated.

The photosensitive resin composition of the present invention contains the near-infrared absorbing group of the present invention. The composition of the compound represented by the general formula (1) described in the near-infrared absorbing substance of the product. The compound represented by the general formula (1) has the same meaning as the compound represented by the general formula (1), and the preferable ranges are also the same.

The photosensitive resin composition of the present invention may contain other components other than the compound represented by the general formula (1) described in the near-infrared absorbing composition, and preferably contains the curable compound. The cured film obtained by curing the photosensitive resin composition of the present invention can be used in a near-infrared cut filter and the like.

[Example]

The following examples illustrate the invention more specifically. The materials, usage amounts, proportions, processing contents, processing sequence, 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 dimethylsulfinium.

(Synthesis example 1) Synthesis of compound I-17

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

0.41 of raw material 1, 0.21 g of trifluorosulfonamide (Tokyo Chemical Co., Ltd.) was dissolved in 20 ml of chloroform, and 0.1 g of triethylamine and dimethylaminopyridine in a catalytic amount were added. Under stirring, the mixture was heated under reflux for 3 days. After cooling, the obtained crude crystals were separated by filtration and purified by silica gel column chromatography (the washing solution was chloroform and methanol) to obtain the target compound (blue solid) I-17. The yield was 55%.

NMR (400MHz, DMSO-d6): δ1.30 (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

Following Synthesis Example 1, compound I-21 was synthesized.

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)

Absorption Spectrum (DMSO) The maximum absorption wavelength is 670nm.

(Synthesis example 3) Synthesis of compound I-22

[Chemical 46]

Following Synthesis Example 1, compound I-22 was synthesized.

NMR (400MHz, DMSO-d6): δ1.23 (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)

Absorption spectrum (DMSO.) The maximum absorption wavelength is 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, 0.19 parts by mass of A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as a polymerizable compound, and photopolymerization Starter IRGACURE OXE 01 (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzidine oxime)], BASF Japan (stock ) Co., Ltd.) 0.09 parts by mass, 0.01 parts by mass of p-methoxyphenol as a polymerization inhibitor, and Megafac F781 (manufactured by Diison Co., Ltd.) as a fluorine-based surfactant, 1.0% propylene glycol monomethyl 0.76 parts by mass of an ether acetate (PGMEA) solution, PGMEA 4.53 as a solvent After mixing and stirring parts by mass, filtration was performed using a nylon filter (manufactured by Pall Corporation, Japan) having a pore diameter of 0.5 μm to prepare a photosensitive resin composition.

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

Comparative compound 1: the following structure

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

[Chemical 49]

Each photosensitive resin composition was applied to a glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film. In addition, the thickness of the coating film was adjusted so that the film thickness (average thickness) became 0.8 μm. Then, the coating film was heat-treated for 120 seconds using a 100 ° C. hot plate.

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

<Heat resistance>

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

The ΔEab value is a value obtained from the following color difference formula obtained from the CIE1976 (L *, a *, b *) space color system (edited by the Japan Color Institute, "New Handbook of Color Science (1985)" , P. 266).

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

<< Judgment Criteria >>

5: △ Eab value <3

4: 3 ≦ △ Eab value <5

3: 5 ≦ △ Eab value <10

2: 10 ≦ △ Eab value <20

1: 20 ≦ △ Eab value

<Lightfastness>

The obtained film was irradiated with 10,000 lux of light through a UV cut filter for 10 hours using an Xe lamp, 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.

<< Judgment Criteria >>

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]

Based on the results, the photosensitive resin compositions of Examples 1 to 3 using the compound of the present invention are excellent in heat resistance and light resistance.

On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 2 containing no compound of the present invention are inferior in heat resistance.

The photosensitive resin composition of Example 1, Comparative Example 1, and Comparative Example 2 was applied to a glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film. In addition, the thickness of the coating film was adjusted so that the film thickness (average thickness) became 0.8 μm. Then, the coating film was subjected to a heat treatment (Prebake) for 120 seconds using a 100 ° C. hot plate.

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

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

A UV-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-technologies) (ref. Glass substrate) was used to measure the heat treatment with only pre-baking. The light transmittance | permeability in the range of the wavelength of 400 nm-1000 nm of the film heated at 200 degreeC or 5 degreeC for 5 minutes.

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

As shown in FIG. 6, it can be seen that the photosensitive resin composition of the present invention sufficiently absorbs light having a wavelength of 700 nm, for example. Moreover, even if it heats at 200 degreeC, the change of an absorption spectrum is small, and it is excellent in heat resistance.

On the other hand, regarding 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, it was not possible to absorb light having a wavelength of 700 nm. In addition, heat resistance is low, and absorption disappears by heating at 130 ° C or higher.

In addition, as shown in FIG. 8, the photosensitive composition of Comparative Example 2 had an H-association peak near a wavelength of 600 nm, and the absorption at a wavelength of 700 nm was small. In addition, during heating, the peaks around 680 nm and 600 nm fluctuated.

(Synthesis Example 4) Synthesis of compound C-15

1.7 g of compound 2 and 3.0 g of compound 3 were added to 10 ml of acetic anhydride, and the mixture was heated and stirred at 120 ° C for 1 hour. Thereafter, ethyl acetate was added to the reaction solution, and the precipitated solid was separated by filtration. To the obtained filtrate, 1.7 g of Compound 2, 0.5 ml of diazabicycloundecene, and 60 ml of acetonitrile were added. The mixture was stirred at room temperature for 3 hours. After hours, a precipitate was obtained by filtration. Next, 0.4 g of the obtained solid was dissolved in 100 ml of methanol, 0.5 g of sodium acetate was added, and the mixture was stirred at room temperature for 2 hours, and then the obtained solid was filtered to obtain the target C-15. The yield was 45%, and the maximum absorption wavelength was 622 nm in dimethyl sulfoxide (DMSO).

<Evaluation of heat resistance and light resistance>

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

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

Table 9 shows the results of the heat resistance and light resistance tests performed on the obtained film by the same method as in Example 1.

From the results, the compound C-15 is excellent in heat resistance and light resistance.

<Synthesis of Copper Complex>

<< Synthesis of Polymer A-1 >>

5.0 g of polyether hydrazone (manufactured by BASF, 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 stream of nitrogen. After reacting at room temperature for 48 hours, the reaction solution was added dropwise to 1 L of a hexane / ethyl acetate (1/1) mixed solution 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 recovered by filtration. The obtained solid was dried under reduced pressure to obtain 4.9 g of polymer A-1. The sulfonic acid group content (meq / g) in the polymer was calculated by neutralization titration. The weight average molecular weight (Mw) was measured by gel permeation chromatography.

<< Synthesis of copper complex Cu-1 >>

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

<Preparation of near-infrared absorbing composition>

The following components were mixed in the following blending amounts 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 hardening 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

Sclerosing compound A: the following compound (Mw; 24,000)

Surfactant A: Olfine E1010 (Nissin Chemical Industry Co., Ltd. (Made in Ltd.)

The copper complex A was synthesized as follows.

A 53.1% sulfophthalic acid aqueous solution (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and the solution was heated to 50 ° C, and 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 generated water were distilled off by an evaporator, thereby obtaining a copper complex A (8.57 g).

<Creating a near-infrared cut filter>

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

In the preparation of the near-infrared absorbing composition, even when the compound I-17 is changed to the compound I-21, the compound I-22, or the compound C-15, the near-infrared absorbing composition 1 can be obtained and used. The same excellent effect of the absorption cut filter. In addition, even if the compound I-17 is changed to Japanese Patent In the cases of D-1 to D-139 described in paragraphs 0049 and later of 2009-263614, the same excellent effects as those of the near-infrared absorption cut-off filter using the near-infrared absorption composition 1 can be obtained.

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

In the preparation of the near-infrared absorbing composition, 5 parts by mass of Polymerizable 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 Kayaku Co., Ltd.), M-305 , M-510, M-520, M-460 (manufactured by East Asia Synthetic), A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.), SR-494 (manufactured by Sadoman Corporation), Denacol EX-212L ( Nagase Chemical Co., Ltd.), JER-157S65 (Mitsubishi Chemical Co., Ltd.). That is, when these circumstances are facilitated, the same excellent effects as those of the near-infrared absorption cut-off filter using the near-infrared absorption composition 1 can be obtained.

In the preparation of the near-infrared absorbing composition, even if the surfactant A is changed to Megafac F171 (manufactured by Diison Co., Ltd.), Sofino (manufactured by Nisshin Chemical Co., Ltd.) In the case of Toray Silicone SF8410 (manufactured by Toray Dow Corning Co., Ltd.), the same excellent effect as that of the near-infrared absorption cut-off filter using the near-infrared absorption composition 1 can be obtained.

Claims (24)

A near-infrared cut-off filter, which contains a near-infrared absorbing substance, has a film thickness of 300 μm or less, and has a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm and a light transmittance of 680 nm or less is 10% or less The near-infrared cut filter contains a compound represented by the following general formula (1) as the near-infrared absorbing substance; In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. A near-infrared cut-off filter, which contains a near-infrared absorbing substance, has a film thickness of 300 μm or less, and has a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm and a light transmittance of 680 nm or less is 10% or less The near-infrared cut filter includes a copper compound as the near-infrared absorbing substance, and the copper compound is at least one selected from the group consisting of a copper-containing copper complex, a copper sulfonate complex, and a copper carboxylate complex. A near-infrared cut-off filter, which contains a near-infrared absorbing substance, has a film thickness of 300 μm or less, and has a light transmittance of 85% or more in a wavelength range of 450 nm to 550 nm, and a light transmittance of 680 nm or less is 10% or less. The near-infrared cut filter contains a compound represented by the following general formula (A) as the near-infrared absorbing substance; In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist. The near-infrared cut filter according to item 2 or 3 of the scope of patent application, further comprising a compound represented by the following general formula (1) as the near-infrared absorbing substance; In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. The near-infrared cut filter according to item 1 of the scope of patent application, wherein the group represented by the general formula (2) is represented by the following general formula (3) or (4); In the general formulae (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group, or an aralkyl group, R ¹² represents a substituent group, and when m is 2 or more, R ¹² may be connected to each other to form a ring, and X represents A 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 a wavy line represents a connection site with the general formula (1). The near-infrared cut filter according to item 1 of the scope of the patent application, wherein R ¹ in the general 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 item 1 or 3 of the scope of the patent application, further comprising a copper compound as the near-infrared absorbing substance, the copper compound being selected from the group consisting of phosphorus-containing copper complex, sulfonic acid At least one of a copper complex and a copper carboxylate complex. The near-infrared cut filter according to item 1 or 2 of the scope of the patent application, which further contains a compound represented by the following general formula (A) as the near-infrared absorbing substance; In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist. The near-infrared cut-off filter according to any one of claims 1 to 3, wherein the film thickness is 200 μm or less. The near-infrared cut-off filter according to any one of claims 1 to 3 in the scope of patent application, wherein the light transmittance in the range of wavelengths from 400nm to 575nm is 85% or more. The near-infrared cut filter according to any one of claims 1 to 3 in the scope of the patent application, wherein the light transmittance in the range of the wavelength of 450 nm to 550 nm is 90% or more. The near-infrared cut-off filter according to any one of claims 1 to 3 in the patent application scope, wherein the light transmittance in the range of wavelengths from 700 nm to 1100 nm is 20% or less. The near-infrared cut-off filter according to any one of claims 1 to 3, wherein the light transmittance in the range of wavelengths from 800 nm to 900 nm is 10% or less. A near-infrared absorbing composition containing a near-infrared absorbing substance and having a transmittance in a wavelength range of 450 nm to 550 nm when forming a film having a thickness of 300 μm or less is 85% or more, and a transmittance in a wavelength of 680 nm is 10% Hereinafter, the near-infrared absorbing composition contains a compound represented by the following general formula (1) as the near-infrared absorbing substance; In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. A near-infrared absorbing composition containing a near-infrared absorbing substance and having a transmittance in a wavelength range of 450 nm to 550 nm when forming a film having a thickness of 300 μm or less is 85% or more, and a transmittance in a wavelength of 680 nm is 10% Hereinafter, the near-infrared absorbing composition contains a copper compound as the near-infrared absorbing substance, and the copper compound is selected from copper complexes containing phosphorus, copper sulfonate complexes, and copper carboxylate complexes. At least one. A near-infrared absorbing composition containing a near-infrared absorbing substance and having a transmittance in a wavelength range of 450 nm to 550 nm when forming a film having a thickness of 300 μm or less is 85% or more, and a transmittance in a wavelength of 680 nm is 10% Hereinafter, the near-infrared absorbing composition contains a compound represented by the following general formula (A) as the near-infrared absorbing substance; In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist. The near-infrared absorbing composition according to item 15 or 16 of the scope of application for a patent, further comprising a compound represented by the following general formula (1) as the near-infrared absorbing substance; In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. The near-infrared absorbing composition according to item 14 or 16 of the scope of the patent application, further comprising a copper compound as the near-infrared absorbing substance, the copper compound being selected from the group consisting of copper-containing copper complex, sulfonic acid At least one of a copper complex and a copper carboxylate complex. The near-infrared absorbing composition according to item 14 or 15 of the patent application scope, which further contains a compound represented by the following general formula (A) as the near-infrared absorbing substance; In the general formula (A), Z ¹ and Z ² are each independently a 5-membered or 6-membered nitrogen-containing heterocyclic non-metal atom group forming a condensable ring, and R ¹ and R ² each independently represent an aliphatic group or Aromatic group, L ¹ represents a methine chain containing an odd number of methine groups, and a and b are independently 0 or 1, and when the site represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c Indicates the number necessary to achieve charge balance. When the site represented by Cy in the formula is an anion, X ¹ represents a cation, and c represents the number necessary to obtain charge balance. When the charge of the indicated site is neutralized in the molecule, X ¹ does not exist. A photosensitive resin composition containing a compound represented by the following general formula (1); In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. A cured film obtained by curing the photosensitive resin composition according to claim 20 of the scope of patent application. A compound represented by the following general formula (1); In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), R ¹ represents an alkyl group having one or more halogen atoms, and 1 An aryl group having more than one halogen atom, or a heterocyclic group having more than one halogen atom; In the general formula (2), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocyclic 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 relationship with the general formula (1) Connection. A camera module includes a solid-state imaging element and a near-infrared cut-off filter according to any one of claims 1 to 13 of a patent application range, which is arranged on a light-receiving side of the solid-state imaging element. A method for manufacturing a camera film group is a method for manufacturing a camera module according to item 23 of the scope of application for a patent, and has a near-infrared cut-off composition coated on the light-receiving side of the solid-state imaging element, thereby forming a near-infrared cutoff In a filter step, the near-infrared absorbing composition contains a near-infrared absorbing substance, and when the film is formed to a thickness of 300 μm or less, the light transmittance in the range of 450 nm to 550 nm is 85% or more, and the light transmittance is 680 nm. The rate is 10% or less.