JP2017014432A - Fluorophenyl group-substituted cyanine compound and near-infrared cut filter comprising the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorophenyl group-substituted cyanine compound that is a novel near-infrared absorbing dye, a thermosetting resin composition prepared with the compound, and a near-infrared cut filter prepared therewith and having excellent heat resistance such as CCD and CMOS.SOLUTION: A near-infrared cut filter is prepared with a fluorophenyl group-substituted cyanine compound that is a novel near-infrared absorbing dye having excellent heat resistance and a thermosetting resin composition comprising epoxy resin as thermosetting resin.SELECTED DRAWING: None

Description

  The present invention relates to a fluorophenyl group-substituted cyanine compound, a thermosetting resin composition containing the compound, and a near-infrared absorption filter (optical filter) having high heat resistance using these compounds.

  Imaging devices such as CCDs (Charge Coupled Devices) and CMOSs (Complementary Metal Oxide Semiconductors) used in digital cameras and the like have spectral sensitivity over the near infrared range from the visible range to about 1100 nm. The human eye can feel light having a wavelength in the vicinity of 400 nm to 700 nm. Therefore, since there is a large difference in spectral sensitivity between the image sensor and the human eye, it is necessary to provide a near-infrared cut filter that absorbs the near-infrared region in front of the image sensor to correct the visual sensitivity of the human eye. It is known.

  As a near-infrared cut filter used for an image sensor, a glass filter in which CuO is added to phosphate glass described in Patent Document 1 is known. However, the glass filter having the near-infrared absorption characteristic is very expensive, has a problem in workability, has a small degree of freedom in designing optical characteristics, and has a complicated response to a spherical surface. In addition, there is a limit to reducing the thickness of the glass filter, and there are problems in securing space and reducing the weight when incorporated in an imaging optical system. Therefore, development of a resin composition having a near-infrared absorption characteristic for producing a new near-infrared cut filter that can be formed into a thin film or a spherical surface is desired.

  Then, development which produces a near-infrared cut filter by coating the coating liquid containing a near-infrared absorption pigment | dye on the surface of an image pick-up element or a filter base material is performed. In Patent Document 2, a near-infrared cut filter using a cyanine compound as a near-infrared absorbing dye is produced, but there is a problem in heat resistance. On the other hand, Patent Document 3 improves heat resistance as compared with conventional products by improving the anion of the cyanine compound.

  However, the heat resistance of the cyanine compound having tris (trifluoromethanesulfonyl) methide anion or the like described in Patent Document 3 as an anion is not sufficient, and development of a near infrared cut filter with higher heat resistance is strongly desired. Therefore, development of a near-infrared absorbing dye and a resin composition for producing the same is strongly demanded.

JP 62-128943 A International Publication 2012/169447 Pamphlet JP 2008-88426 A

  An object of this invention is to provide the thermosetting resin composition for producing the novel near-infrared absorption pigment | dye excellent in heat resistance, and the near-infrared cut filter containing the pigment | dye.

  As a result of intensive studies, the present inventors have devised a thermosetting resin composition containing a novel cyanine compound having a fluorophenyl group and a thermosetting resin, and a near-infrared cut filter using the same. It has been found that the above-mentioned problems can be solved, and the present invention has been completed.

（式中、Ｒ_１はそれぞれ独立に炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシアルキル基を示し、ｎは１〜５の整数であり、結合基Ｄは下記式（２）又は式（３）のいずれかであり、Ｙは水素原子、塩素原子、アシルオキシ基、炭素数１〜５のアルキル基又はフェニル基のいずれかであり、＊は結合部位を示し、Ｘ⁻はトリス（トリフルオロメタンスルホニル）メチドアニオンである。）

[２]式（１）におけるｎが１〜３の整数であることを特徴とする［１］に記載のフルオロフェニル基置換シアニン化合物、
[３]式（１）におけるｎが２であることを特徴とする［１］又は［２］に記載のフルオロフェニル基置換シアニン化合物、
[４]式（１）が下記式（４）であることを特徴とする［１］乃至［３］のいずれか一つに記載のフルオロフェニル基置換シアニン化合物、

（式中、Ｒ_１、Ｄ、Ｘ⁻は式（１）と同義である。）
[５]式（２）におけるＹが塩素原子、メチル基、アセトキシ基又はフェニル基であることを特徴とする[１]乃至[４]のいずれか一つに記載のフルオロフェニル基置換シアニン化合物、
[６]式（３）におけるＹが水素原子又はフェニル基であることを特徴とする[１]乃至[５]のいずれか一つに記載のフルオロフェニル基置換シアニン化合物、
[７]式（１）及び式（４）におけるＲ_１がメチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、又はメトキシエチル基であることを特徴とする[１]乃至[６]のいずれか一つに記載のフルオロフェニル基置換シアニン化合物、
[８]近赤外線吸収色素として[１]乃至[７]のいずれか一つに記載の化合物を少なくとも1種類含むことを特徴とする熱硬化性樹脂組成物、
[９]熱硬化性樹脂としてエポキシ樹脂を含むことを特徴とする[８]に記載の熱硬化性樹脂組成物、
[１０]エポキシ樹脂がフルオレン骨格を有することを特徴とする[９]に記載の熱硬化性樹脂組成物、
[１１]エポキシ樹脂が下記式（５）で表される構造を有することを特徴とする[１０]に記載の熱硬化性樹脂組成物、

（式中、環Ｚはそれぞれ独立したベンゼン環を含む縮合多環式芳香族炭化水素環、Ｒ_４及びＲ_５はそれぞれ独立にシアノ基、ハロゲン原子、アルキル基、アリール基から選ばれ、Ｒ_６はそれぞれ独立して水素原子又はメチル基を示し、ｎは０〜１の整数、ｘは０〜４の整数、ｙは０以上の整数、ｚは１以上の整数である。）
[１２]式（５）において２つの環Ｚが共にベンゼン環であることを特徴とする［１１］に記載の熱硬化性樹脂組成物、
[１３][１]乃至[１２]のいずれか一つに記載の熱硬化性樹脂組成物の硬化物、
[１４][１]乃至[１３]のいずれか一つに記載の熱硬化性樹脂組成物より得られる近赤外線カットフィルタ、
[１５][１４]に記載の近赤外線カットフィルタを具備した撮像素子、
に関する。 That is, the present invention
[1] A fluorophenyl group-substituted cyanine compound represented by the following formula (1):

(In the formula, R ₁ is each independently an alkoxyalkyl group of 1 to 5 alkyl or C1-5 atoms, n is an integer of 1 to 5, the linking group D represents the following formula (2) Or Y is a hydrogen atom, a chlorine atom, an acyloxy group, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, * indicates a bonding site, and X ⁻ is a tris. (Trifluoromethanesulfonyl) methide anion.)

[2] The fluorophenyl group-substituted cyanine compound according to [1], wherein n in the formula (1) is an integer of 1 to 3.
[3] The fluorophenyl group-substituted cyanine compound according to [1] or [2], wherein n in the formula (1) is 2.
[4] The fluorophenyl group-substituted cyanine compound according to any one of [1] to [3], wherein the formula (1) is the following formula (4):

(In the formula, R ₁ , D and X ⁻ have the same meanings as in formula (1).)
[5] The fluorophenyl group-substituted cyanine compound according to any one of [1] to [4], wherein Y in the formula (2) is a chlorine atom, a methyl group, an acetoxy group, or a phenyl group,
[6] The fluorophenyl group-substituted cyanine compound according to any one of [1] to [5], wherein Y in formula (3) is a hydrogen atom or a phenyl group,
[7] R ₁ in formula (1) and formula (4) is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl A fluorophenyl group-substituted cyanine compound according to any one of [1] to [6], which is a group or a methoxyethyl group,
[8] A thermosetting resin composition comprising at least one compound according to any one of [1] to [7] as a near-infrared absorbing dye,
[9] The thermosetting resin composition according to [8], comprising an epoxy resin as the thermosetting resin,
[10] The thermosetting resin composition according to [9], wherein the epoxy resin has a fluorene skeleton,
[11] The thermosetting resin composition according to [10], wherein the epoxy resin has a structure represented by the following formula (5):

(Wherein ring Z is independent fused polycyclic aromatic hydrocarbon ring containing a benzene ring, R ₄ and R ₅ independently represent a cyano group, a halogen atom, an alkyl group, selected from an aryl group, R ₆ Each independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 1, x is an integer of 0 to 4, y is an integer of 0 or more, and z is an integer of 1 or more.)
[12] The thermosetting resin composition according to [11], wherein the two rings Z in the formula (5) are both benzene rings,
[13] A cured product of the thermosetting resin composition according to any one of [1] to [12],
[14] A near infrared cut filter obtained from the thermosetting resin composition according to any one of [1] to [13],
[15] An image pickup device comprising the near infrared cut filter according to [14],
About.

  According to the present invention, a thermosetting resin composition capable of producing a near-infrared cut filter excellent in heat resistance can be provided.

  The present invention relates to a thermosetting resin composition comprising a near-infrared absorbing dye of a novel fluorophenyl group-substituted cyanine compound represented by the following formula (1) and a thermosetting resin such as an epoxy resin.

In the formula (1), R ₁ represents an alkoxyalkyl group of 1 to 5 alkyl or C1-5 atoms independently.

In R ₁ of formula (1), the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. , Iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group and the like.

In R ₁ of formula (1), the alkoxyalkyl group having 1 to 5 carbon atoms is not particularly limited, but is a methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, n-butoxyethyl group. Group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group and the like.

In R ₁ of formula (1), the alkyl group having 1 to 5 carbon atoms may have a substituent, and the substituent is not particularly limited, but examples thereof include an alkoxy group and an alkyl group. An alkoxyalkyl group in which hydrogen is substituted with an alkoxy group, an alkoxyalkoxyalkyl group in which an alkoxyalkoxy group is substituted, an alkoxyalkoxyalkoxyalkyl group in which an alkoxyalkoxyalkoxy group is substituted; a substituted or unsubstituted amino group (alkylaminoalkyl) Group, dialkylaminoalkyl group), alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, halogen atom, amino group, cyano group and the like. Examples of the substituent in which the alkyl group is halogenated include chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group. Etc. R ₁ is preferably an ethyl group, an n-propyl group, an n-butyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group or an n-butoxyethyl group, particularly preferably an ethyl group, an n-butyl group or a methoxyethyl group. preferable.

In R ₁ of formula (1), the alkoxyalkyl group having 1 to 5 carbon atoms may have a substituent, and the substituent is not particularly limited, but an alkoxy group, an alkoxyalkoxy group, Alkoxyalkoxyalkoxy groups and the like; Halogen atoms, substituted or unsubstituted amino groups (dialkylamino groups and the like), alkoxycarbonyl groups, alkylaminocarbonyl groups, alkoxysulfonyl groups and the like.

  N of Formula (1) is an integer of 1-5, 2-5 are preferable and 2 is especially preferable.

X ^{− in the} formula (1) is particularly preferably tris (trifluoromethanesulfonyl) methide anion from the viewpoint of heat resistance of the cured product (near infrared cut filter).

  The linking group D in the formula (1) is represented by the following formula (2) or the formula (3), and * represents a binding site. Y in Formula (2) and Formula (3) is any one of a hydrogen atom, a chlorine atom, an acyloxy group, an alkyl group having 1 to 5 carbon atoms, and a phenyl group, and among them, a hydrogen atom, a chlorine atom, a methyl group, and an acetoxy group Or a phenyl group is preferable.

  In Y in the formulas (2) and (3), the acyloxy group means a group (RCOO-) obtained by removing a hydrogen atom from a carboxyl group of a carboxylic acid, and is not particularly limited. Group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group and the like, and an acetoxy group is preferable.

  In Y in Formula (2) and Formula (3), the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, Examples include n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, and the like, methyl group Is preferred.

  In Y in Formula (2) and Formula (3), the phenyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, and n- Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, fluoro group, trifluoromethyl group, methoxy group, ethoxy group, propoxy group, nitro group, cyano group Etc.

  The near-infrared absorbing dye of the present invention is more preferably a fluorophenyl group-substituted cyanine compound having a cation moiety represented by the above formula (1), and the following formula (4) having the formula (2) and formula (3) as a linking group D: A fluorophenyl group-substituted cyanine compound having a cation moiety represented by

（式中、Ｒ_１、Ｄ及びＸ⁻は式（１）におけるのと同義である。）

(Wherein R ₁ , D and X ⁻ have the same meanings as in formula (1).)

  The compound represented by the above formula (1) of the present invention can be synthesized by, for example, the following method with reference to Patent Document 3.

[Synthesis step 1]
1 mol of a compound represented by the following formula (6) and 1 mol of methyl isopropyl ketone are heated in an organic solvent such as ethanol, for example, at 20 ° C. to 130 ° C. for 30 minutes to 5 hours as necessary in the presence of an acid catalyst. An indolenine compound represented by the following formula (7) can be synthesized.

（式中、Ｘはハロゲン基又はトリフラート基である。）

(In the formula, X is a halogen group or a triflate group.)

  The acid catalyst for synthesizing the indolenine compound represented by the above formula (7) is not particularly limited, and examples thereof include hydrochloric acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, and p-toluenesulfonic acid pyridinium. .

[Synthesis step 2]
1 mol of the compound represented by the above formula (7) and 1 mol of a fluorophenyl compound having boronic acid (or boronic acid ester) as a reactive group, and using a palladium catalyst and a base, if necessary, such as toluene and alcohol A compound represented by the following formula (8) can be synthesized using an Suzuki coupling reaction (see “Metal-Catalyzed Cross-Coupling Reactions-Second, Completely Revised and Enlarged Edition”) in an organic solvent or water. it can.

Specific examples of the palladium catalyst used in the Suzuki coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (Dba) ₃ · CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-t-butylphosphino) palladium (0): Pd (t-Bu ₃ P) ₂ , [ 1,1′-bis (diphenylphosphino) ferrocene] palladium (II) di Chloride: Pd (dppf) Cl ₂ , or [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1): Pd (dppf) Cl ₂ .CH ₂ Cl ₂ Can be mentioned.

  Moreover, in order to promote reaction, you may add a phosphine compound to these palladium compounds as needed. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N -Dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1'-bis (di-t-butylphosphino) ) Ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, etc. Can be mentioned.

  Specific examples of the base used include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, potassium acetate, phosphorus Examples include tripotassium acid or potassium fluoride.

[Synthesis step 3]
1 mole of the compound represented by the above formula (8) and 1 mole of an alkylating agent having 1 to 5 carbon atoms having a leaving group such as a halogeno group or a tosyl group, or 1 mole of an alkoxyalkylating agent having 1 to 5 carbon atoms. The compound represented by the following formula (9) can be synthesized by heating in an organic solvent such as acetonitrile as necessary, for example, usually at 20 to 150 ° C. for 1 to 5 hours.

A ^{− in} formula (9) is an anion derived from the leaving group of the alkylating agent or alkoxyalkylating agent used in the above synthesis, and the alkylating agent and the alkoxyalkylating agent have a substituent. The substituent and R _{1 in} formula (9) are as defined in formula (1).

  2 moles of the compound represented by the above formula (9), 1 mole of the compound represented by the following formula (10) or formula (11), and tris (trifluoromethanesulfonyl) methido acid or a sodium salt or potassium salt thereof 1 mol of the salt is optionally added in an organic solvent such as ethanol, acetic anhydride or a mixture of acetic anhydride and glacial acetic acid in the presence of a base catalyst such as sodium acetate, potassium acetate, piperazine, piperidine, triethylamine, etc. The compound represented by the formula (1) can be synthesized by heating and condensing at ˜140 ° C. for usually 10 minutes to 10 hours, preferably 30 minutes to 4 hours.

（式（１０）及び式（１１）の結合基Ｄは式（１）におけるのと同義である。）

(The linking group D in the formulas (10) and (11) has the same meaning as in the formula (1).)

  Specific examples of the solvent used in the above synthesis steps 1 to 3 include benzene, toluene, xylene, 1,2,4-trimethylbenzene, acetonitrile, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, and t-butylmethyl. Organic solvents such as ether, 1,4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropyl alcohol, glacial acetic acid, acetic anhydride and the like can be selected, and these solvents can be selected as appropriate and may be used alone or as a mixed solvent. .

  Although the specific example represented by the said Formula (1) of this invention is illustrated to the compounds 1-36, this invention is not limited to these.

  The near-infrared cut filter of the present invention is obtained by a thermosetting resin composition containing at least the cyanine compound of the present invention having a near-infrared absorption characteristic and a thermosetting resin. Moreover, you may add near-infrared absorption pigment | dyes other than said Formula (1) as needed for the objective, such as adjustment of a near-infrared absorption area | region.

  Examples of the thermosetting resin used in the present invention include an epoxy resin, a urethane resin, a cyanate resin, a phenol resin, and an amide resin. Any of these can be used in the present invention, but considering the curability and heat resistance required for the thermosetting resin, an epoxy resin or an amide resin is preferable, and further considering transparency, the epoxy resin alone, or In order to accelerate curing, it is more preferable to combine an epoxy resin curing agent as necessary.

  First, the urethane resin used in the present invention will be described below, but any compound may be used as long as it is a compound containing a urethane group in the molecule.

  Examples of the urethane resin include a urethane resin obtained by reacting a polyisocyanate with a compound having two or more alcoholic hydroxyl groups.

  For example, various polyisocyanates known per se can be used as the polyisocyanate, and the polyisocyanate is not limited to a specific compound. Examples of the polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o, m, or p) -xylene diisocyanate, (o, m, or p) -hydrogenated xylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate and the like.

  Examples of the compound having two or more alcoholic hydroxyl groups include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, diethylene glycol, triethylene glycol, Ethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,2-dodecanediol, 1,2- Octadecanediol, adamantanediol, adamantanetrio Le, octahydro-1H-4,7-methanolate indene-diol, octahydro-1H-4,7-meth Noin Denis distearate methanol, and the like.

  Any cyanate resin may be used as long as it is a compound containing a cyanate group in the molecule. For example, novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethyl Examples thereof include bisphenol type cyanate resins such as bisphenol F type cyanate resin and partially triazine-modified prepolymers.

  The phenol resin used in the present invention may be a thermosetting resin obtained by condensation of a compound having a phenolic hydroxyl group and an aldehyde compound. Various types of phenol and aldehyde compounds known per se can be used and are not limited to specific compounds. Examples of the aldehyde compound include glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and the like.

  Examples of the compound having a phenolic hydroxyl group include phenol, orthocresol, metacresol, paracresol, orthoethylphenol, metaethylphenol, paraethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5- Xylenol, 3,5-xylenol, 2,6-xylenol, orthobutylphenol, metabutylphenol, parabutylphenol, orthooctylphenol, metaoctylphenol, paraoctylphenol, orthononylphenol, metanonylphenol, paranonylphenol, orthophenylphenol, metaphenylphenol, para Phenylphenol, orthocyclohexylphenol, metacyclohexylphenol, paracyclohexylphenol, Tekoru, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, hydroquinone, and the like.

  The amide resin used in the present invention may be a thermosetting resin obtained by polycondensation of a dicarboxylic acid compound and an amine compound. Various carboxylic acid compounds and amine compounds known per se can be used and are not limited to specific compounds.

  Examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl. Succinic acid, azelaic acid, sebacic acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid Acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid , Cyclohexane-1,2,4-tricarboxylic acid, 1,2,3 propane tricarboxylic acid, citric acid, isocitric acid, 1,3,5-benzenetricarboxylic acid.

  Examples of the amine compound include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 1, 8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1,12-dodecanediamine, 2,2, 4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine , M-xylenediamine, 4,4'-diaminodiphenyl Tan, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, bis (hexamethylene) triamine, 1,2,4-benzene triamine, triethylene tetramine and the like.

  Hereinafter, the epoxy resin suitably used in the present invention will be described in detail. The epoxy resin is not particularly limited as long as it is a compound having an epoxy group in the molecule, but is mainly classified into an aliphatic type epoxy resin and an aromatic type epoxy resin.

  Examples of the aliphatic epoxy resin include an epoxy resin having an aliphatic cyclic structure and an epoxy resin having no aliphatic cyclic structure. An epoxy resin having an aliphatic cyclic structure is one having at least one aliphatic cyclic structure in one molecule, such as terpene diphenol, phenol compounds (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene). , Dihydroxynaphthalene, etc.) and polycyclic condensates of aliphatic ring structure dienes (dicyclopentadiene, norbornadiene, hexahydroxyindene, etc.), and glycidyl etherified products derived from these modified products, hydrogenated bisphenols (bisphenol A, bisphenol F). ) Type epoxy resin, alicyclic epoxy resin and the like, and epoxy resin having a cyclohexyl structure, dicyclopentadiene structure and triglycidyl isocyanurate structure in the molecule.

  Examples of the epoxy resin having no aliphatic cyclic structure include a glycidyl ether compound derived from a linear or branched alcohol such as hexane diglycidyl ether and a resin having a methacryl glycidyl skeleton.

  The resin having a methacrylic glycidyl skeleton is not particularly limited, and examples thereof include a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, and is available from the market. Examples of such products include Marproof G-0115S, G-0130S, G-0250S, G-1010S, G-1005S, G-0150M, and G-2050M (manufactured by NOF Corporation). . Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, and vinyl-substituted aromatic compounds, such as methyl (meth) acrylate and ether (meth) acrylate. , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane, and the like, and methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, and styrene are particularly preferable.

  Aromatic epoxy resins include cresol novolac epoxy resin, phenol novolac epoxy resin, novolak epoxy resin such as naphthol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, etc. Bisphenol type epoxy resin, trisphenol methane type epoxy resin, glyoxal type epoxy resin, (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) α, α-dimethylbenzyl) phenol) type epoxy resin, fluorene Examples thereof include an epoxy compound having a skeleton. In the present invention, an epoxy resin having a fluorene skeleton of the following formula (5) (hereinafter abbreviated as fluorene) is preferably used in consideration of heat resistance. You may use the epoxy resin represented by Formula (5) 1 type or in mixture of 2 or more types.

  The condensed polycyclic aromatic hydrocarbon ring represented by the ring Z in the formula (5) is a condensed bicyclic hydrocarbon ring (for example, a condensed bicyclic hydrocarbon having 8 to 20 carbon atoms such as an indene ring or a naphthalene ring). Condensed bicyclic to tetracyclic hydrocarbon rings such as a hydrocarbon ring, preferably a condensed bicyclic hydrocarbon ring having 10 to 16 carbon atoms), a condensed tricyclic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.), etc. Is mentioned. Preferred examples of the condensed polycyclic aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is particularly preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and are usually preferably the same ring.

  The substitution position of the ring Z substituted at the 9-position of fluorene is not particularly limited. For example, when the condensed polycyclic aromatic hydrocarbon ring substituted at the 9-position of fluorene is a naphthalene ring, a 1-naphthyl group, 2 -A naphthyl group etc. may be sufficient and 2-naphthyl group is especially preferable.

R _{4 in} formula (5) is, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (carbon number 6-10 such as phenyl group, etc.). Non-reactive substituents such as an aryl group) and the like], a halogen atom, a cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable. As the alkyl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group (for example, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group Are particularly preferred). In addition, when the number of substituents x is plural (two or more), R ₄ substituted on two benzene rings constituting fluorene (or fluorene skeleton) may be the same or different, and the bonding position (substitution position) of R ₄ ) Is not particularly limited. The number of substituents x with respect to the benzene ring constituting the fluorene may be the same or different from each other, but is preferably 0 to 1, particularly preferably 0.

R ₅ substituted on ring Z is, for example, an alkyl group (for example, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and having 1 to 8 carbon atoms). An alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable), a cycloalkyl group (for example, a cycloalkyl group having 5 to 8 carbon atoms such as a cyclohexyl group, and a cycloalkyl having 5 to 6 carbon atoms). Group is preferable), an aryl group (for example, an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group and a xylyl group, preferably an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 to 8 carbon atoms) Are more preferred), hydrocarbon groups such as aralkyl groups (aryl groups having 6 to 10 carbon atoms such as benzyl and phenethyl groups); alkoxy groups (for example, An alkoxy group having 1 to 8 carbon atoms such as a toxi group, preferably an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group (such as a cycloalkyloxy group having 5 to 10 carbon atoms), an aryloxy group (having a carbon number) 6 to 10 aryloxy groups, etc.)-OR ₇ [wherein R ₇ represents a hydrocarbon group (such as the hydrocarbon group exemplified above). ]; Alkylthio group (e.g., an alkylthio group having 1 to 8 carbon atoms such as a methylthio group, an alkylthio group preferably having 1 to 6 carbon atoms) in the radical -SR ₇ (wherein such, _{R 7} are as defined above. ); Acyl group (acyl group having 1 to 6 carbon atoms such as acetyl group); alkoxycarbonyl group (such as alkoxy substituted carbonyl group having 1 to 4 carbon atoms such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom) , Bromine atom, iodine atom, etc.); hydroxyl group; nitro group; cyano group; substituted amino group (for example, dialkylamino group such as dimethylamino group) and the like.

Of these, R ₅ is preferably a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, halogen atom, nitro group, cyano group, substituted amino group, etc. Hydrogen group [eg, alkyl group (eg, alkyl group having 1 to 6 carbon atoms)], alkoxy group (such as alkoxy group having 1 to 4 carbon atoms), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) And the like are particularly preferable.

R ₅ of the two rings Z may be the same or different. In the same ring Z, when the number of substituents y of R ₅ is 2 or more, they may be the same as or different from each other. The number y of substituents is usually 0 to 8, preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2. In the two rings Z, the number of substituents y may be the same or different from each other.

R _{6 in the} formula (5) is a hydrogen atom or a methyl group, and preferably a hydrogen atom.

  The substituent number z of the substituent having an epoxy group of formula (5) (referred to as glycidyloxy group) may be 1 or more, usually 1 to 4, preferably 1 to 3, more preferably 1 to 2, 1 is particularly preferred. In addition, the number z of substituents may be the same or different in each ring Z, and is usually the same in many cases. In addition, the substitution position on the ring Z of a glycidyloxy group is not specifically limited, What is necessary is just to substitute to the suitable substitution position of the ring Z.

  The number n of ethyleneoxy chains in the glycidyloxy group of the formula (5) is an integer of 0 to 1, preferably 0. In addition, although n may be the same or different in each ring Z, the same integer is preferable.

  The substitution position of the single or plural glycidyloxy groups on the ring Z is not particularly limited with respect to the position bonded to the 9 position of the fluorene of the ring Z. For example, when the ring Z is a benzene ring, the ortho position , Meta position, para position and the like, and para position is particularly preferable. When the condensed polycyclic aromatic hydrocarbon ring substituted at the 9-position of fluorene is a naphthalene ring, the ortho-position, meta-position, para-position, ana-position, epi-position, cata-position, peri-position, pros-position, amphi-position, It may be in the 2nd and 7th positions, and the amphi position is particularly preferred.

  Specific examples of the compound represented by the formula (5) include 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9- Bis (3-glycidyloxyphenyl) fluorene and the like], 9,9-bis (glycidyloxynaphthyl) fluorene [eg, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5 -Glycidyloxy-1-naphthyl) fluorene and the like], and the like, a compound in which the number of substituents z in formula (5) is 1 and n is 0 is exemplified.

  The epoxy equivalent of the epoxy compound having a fluorene skeleton is preferably 150 to 1000 g / eq., More preferably 150 to 800 g / eq., Further preferably 150 to 400 g / eq., And particularly preferably 150 to 350 g / eq. . These are easily available from the market, and examples thereof include Ogsol PG-100 and Ogsol CG-500 manufactured by Osaka Gas Chemical Co., Ltd.

  The thermosetting resin used in the present invention is most preferably an epoxy resin represented by the above formula (5), but may contain other epoxy resins as long as the effects of the present invention are not impaired. Other epoxy resins include glycidyl ether type epoxy resins such as bisphenol type epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.), phenol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene modified Phenol (or cresol) novolac type epoxy resin, biphenyl type epoxy resin, triphenolalkane type epoxy resin (triphenolmethane type epoxy resin, etc.), phenol aralkyl type epoxy resin, heterocyclic type epoxy resin (epoxy resin containing xanthene unit) ), Stilbene type epoxy resin, condensed ring aromatic hydrocarbon modified epoxy resin (1,6-bis (glycidyloxy) naphthalene, bis (2,7-bis (glycidyloxy)) Futaren) naphthalene ring-containing epoxy resin of the alkane or the like), glycidyl ester type epoxy resin, other epoxy resins having a fluorene skeleton. These other epoxy resins may be used alone or in combination of two or more.

  When other epoxy resins are used, the ratio of the compound represented by the above formula (5) to the whole epoxy resin component is usually 50 to 99.5% by weight, preferably 70 to 97% by weight, and 90 to 90%. More preferred is 98% by weight.

  The epoxy resin curing agent used in the present invention is not particularly limited as long as it exhibits a curing acceleration effect of the epoxy resin, but has two or more functional groups capable of reacting with the epoxy resin in one molecule. The carbon number constituting the epoxy resin curing agent is usually 2 to 200, preferably 2 to 80, more preferably 3 to 60, and particularly preferably 4 to 40. Also, known epoxy resin curing agents can be used, for example, carboxylic acid curing agents having a carboxyl group or a carboxylic anhydride group, amino groups, amide groups, ketoimine groups, imidazole groups, dicyandiamide groups, etc. Examples thereof include amine-based curing agents and phenol-based curing agents having a phenol group such as phenol novolac, and carboxylic acid-based curing agents are preferable from the viewpoint of heat resistance and transparency of the cured product.

  The carboxylic acid-based curing agent is not particularly limited as long as it has one or more, preferably two or more, or one or more carboxylic anhydride groups in the molecule. Can be used. In the present invention, a carboxylic acid anhydride, a polyvalent carboxylic acid, or the like can be used.

  Specific examples of carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro anhydride Phthalic acid, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2 , 3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc. Examples include acid anhydrides having 4 to 40 carbon atoms in the skeleton constituting the anhydride. In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-diethylglutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2, 1] Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Etc. are preferable from the viewpoint of light resistance, transparency, and workability.

  The polyvalent carboxylic acid is a compound having at least two carboxyl groups, and is not particularly limited when these compounds have geometric isomers or optical isomers. The polyvalent carboxylic acid is preferably a bifunctional or higher carboxylic acid, such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid. Alkyltricarboxylic acid compounds such as citric acid; aliphatic cyclic polyvalent compounds such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid, and methylnadic acid Carboxylic acid compounds; dimer acid compounds which are multimers of unsaturated fatty acids such as linolenic acid and oleic acid and their reduction products; malic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid , Nonanedioic acid, linear alkyl diacid compound of decanedioic acid, bicyclo [2,2,1] hepta -2,3-dicarboxylic acid, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid, octahydro-1H-4,7-methanoindene-2,5 -The polyvalent carboxylic acid compound which has bicyclo structures, such as dicarboxylic acid, etc. are mentioned.

  Moreover, the polyhydric carboxylic acid obtained by making commercially available bifunctional or more than trifunctional alcohol compound react with an acid anhydride or polyhydric carboxylic acid can also be used. Examples of the acid anhydride or polyvalent carboxylic acid include the above-mentioned compounds. As the alcohol compound, the geometric isomer or optical isomer is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,5-hexanediol. , Diethylene glycol, triethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,2-propanediol, neopentyl glycol, 1 , 2-butanediol, 1,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 3- Methyl-1,5-pentanediol 2 carbon atoms such as 1,2-dodecanediol, 1,2-octadecanediol, adamantanediol, adamantanetriol, octahydro-1H-4,7-methanoindenediol, octahydro-1H-4,7-methanoindenyldimethanol ˜30 organic aliphatic alcohol compounds.

  When the curing agent other than the above-mentioned acid anhydride and / or polyvalent carboxylic acid is used as the epoxy resin curing agent, the ratio of the total weight of the acid anhydride and / or polyvalent carboxylic acid in the total curing agent is 30 weight% or more is preferable and 40 weight% or more is especially preferable.

  Examples of the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like, and specific examples thereof include amine compounds (1,4-butanediamine, etc.) and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, Triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, polyphenol compounds (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol) 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphth Thallenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenolic compounds (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxy Naphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 '-Biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, etc. Examples include polycondensates and modified products thereof, halogenated bisphenol compounds such as tetrabromobisphenol A, condensates of terpenes and phenol compounds, and others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc.) However, these are not limited, and these may be used alone or in combination of two or more.

  In the thermosetting resin composition of the present invention, the hardness of the cured product can be supplemented by using a coupling agent as necessary. Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercapto Propyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 Silane coupling agents such as chloropropyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate , Titanium-based coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneo Decanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neo Examples thereof include zirconium such as alkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, and aluminum coupling agents. These coupling agents may be used alone or in combination of two or more. Although a coupling agent is used as needed, it is 0.05-20 weight% normally with respect to the total weight of the thermosetting resin composition of this invention, Preferably 0.1-10 weight% is added.

  In the thermosetting resin composition of the present invention, it is possible to supplement mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. The average particle size of the inorganic filler used is usually 500 nm or less, and 200 nm or less is preferable in consideration of the transparency of the cured product. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. These inorganic fillers are suitably used in the range of 0 to 95% by weight with respect to the total weight of the thermosetting resin composition of the present invention.

  In order to prevent coloration of the near-infrared cut filter produced from the thermosetting resin composition of the present invention, an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant can be contained. .

  Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6, 6-totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol And 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (2,2) decanedioate , 6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetra Til-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] Tilmalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N" '-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazi -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / Tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7 - Oxa-3,20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidinyl), benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1 3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5 -Methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) Benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazole-2- Yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds, , 4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) Examples include triazine compounds such as -5-[(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

  The following commercially available products can be used as the amine compound that is the light stabilizer. The commercially available amine compound is not particularly limited. For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, manufactured by ADEKA, LA-52, LA-57, LA, manufactured by Ciba Specialty Chemicals, Inc. -62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound as the antioxidant is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol di- Phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol Diphosphite, dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert) -Butyl fluoride Nyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-) tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) Phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6- tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) ) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) −3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4 , 3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl -Phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6 Di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) ) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, tri Phenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. And the like.

  A commercial item can also be used for said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, ADEKA company make, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, Adekas tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP, and the like.

  One phenolic compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy. Phenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexane Diol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pe Taerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butyl) Phenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) Bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di- tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for said phenolic compound. The commercially available phenolic compounds are not particularly limited, and examples thereof include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, IRGANOX 1520A made by Ciba Specialty Chemicals; -20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330; Sumilizer GA-80, Sumilizer MDP-S, Sumili zer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. are mentioned.

  In addition, a commercially available additive can be used as a resin anti-coloring agent, and examples thereof include THINUVIN328, THINUVIN234, THINUVIN326, THINUVIN120, THINUVIN477, THINUVIN479, CHIMASSORB2020FDL, and CHIMASSORB119FL manufactured by Ciba Specialty Chemicals. .

  As an additive that can be used together as necessary, it is preferable to contain at least one selected from the above amine compounds, phosphorus compounds, and phenol compounds, and the addition rate is not particularly limited, but the heat of the present invention The range of 0.005 to 5.0 weight% is preferable with respect to the total weight of the curable resin composition.

  In order to improve the curing speed when producing the near infrared cut filter of the present invention, a curing accelerator can be contained. The curing accelerator can be selected according to the type of the curing agent, for example, an amine compound [for example, a tertiary amine compound (for example, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino)). Methyl) phenol, 1,8-diazabicyclo (5.4.0) undecene-1, etc.), imidazole compounds (eg, alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole) and derivatives thereof ( For example, salts such as phenol salts, phenol novolak salts, carbonates, formates, etc.)], alkali metal or alkaline earth metal alkoxides, phosphine compounds (such as triphenylphosphine), amide compounds (such as dimer acid polyamide), Lewis acids Complex compound Boron trifluoride / ethylamine complex, etc.), sulfur compounds [polysulfide, mercaptan compounds (thiol compound), etc.], boron compounds (phenyldichloroborane, etc.), condensable organometallic compounds (organic titanium compounds, organoaluminum compounds, etc.), etc. Can be mentioned. You may use a hardening accelerator individually or in combination of 2 or more types.

  The addition rate of the curing accelerator is usually 0.001 to 30 parts by weight and 0.05 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin (or epoxy resin component) represented by the above formula (5). Preferably, 0.1-10 weight part is further more preferable.

  If necessary, the thermosetting resin composition of the present invention may be a reactive diluent such as a monofunctional epoxy compound, a diluent such as a solvent, or a colorant or stabilizer (a heat stabilizer, an antioxidant, UV additives, etc.), fillers, antistatic agents, flame retardants, flame retardant aids and the like may be included. Diluents and additives may be used alone or in combination of two or more.

  The near-infrared cut filter (optical filter) using the thermosetting resin composition of the present invention may be provided on a substrate or the substrate itself. Although it will not restrict | limit especially if it can generally be used for an optical filter as a base material, Usually, a glass or resin-made base material is used. The thickness of the near-infrared cut layer is usually about 0.05 μm to 10 mm, but is appropriately determined according to the purpose such as the near-infrared cut rate. Further, an image pickup device itself such as a CCD or CMOS can be used as a base material.

  Examples of the resin base material used in the present invention include polyethylene, polycycloalkane, polycycloolefin, polystyrene, polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride. Vinyl compounds such as, and addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / Vinyl compounds such as tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer or copolymers of fluorine-based compounds, polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Resin containing iodine, nylon 6, polyamide such as nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polycarbonate, polyether polyoxymethylene or the like, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like.

  A method for producing a near-infrared cut filter (optical filter) using the thermosetting resin composition of the present invention is not particularly limited. For example, 1) a near-infrared absorbing dye for a thermosetting resin and a curing agent. A method for producing a resin plate or film by heating and curing after molding, 2) a thermosetting resin composition containing a near infrared absorbing dye, a transparent resin plate, transparent Method for coating film, transparent glass plate, or image pickup device 3) A thermosetting resin composition containing the near-infrared absorbing dye of the present invention and a resin (adhesive) is prepared, and a laminated resin plate and a laminated resin film Alternatively, a known method such as a method for producing a laminated glass plate can be used.

  In the method 1), the near-infrared absorbing dye of the present invention is dissolved in a thermosetting resin and a curing agent and injected into a mold and heated to react to be cured, or poured into a mold and hardened in the mold. A method of forming by heating reaction until a product is obtained. Depending on the composition used, the processing temperature, filming (resin plate) conditions and the like are somewhat different, but usually curing conditions of 100 to 200 ° C. for about 30 minutes to 5 hours are applied. The addition amount of the near-infrared absorbing dye of the present invention is appropriately determined according to the target near-infrared cut rate, and varies depending on the thickness of the resin plate or film to be produced, absorption intensity, visible light transmittance, etc. It is used in an amount of about 0.01 to 30% by weight, preferably about 0.01 to 15% by weight, based on the weight of the base resin.

  The method 2) is a method in which a near-infrared absorbing dye is dissolved in a binder resin to form a paint, and a solvent can be used in forming the paint. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixed solvent thereof can be used. Although the density | concentration of the near-infrared absorptive pigment | dye of this invention changes with thickness, absorption intensity, and visible light transmittance | permeability of the coating to produce, it is generally about 0.01-30 weight% with respect to binder resin. The coating material thus obtained is coated on a transparent resin plate, transparent film, transparent glass plate, or imaging device with a spin coater, bar coater, roll coater, gravure coater, offset coater, spray, etc. A cut filter or an image sensor including the cut filter can be obtained.

  3) The near infrared absorption of the present invention is applied to known transparent adhesives for laminated glass such as silicon-based, urethane-based, acrylic-based resins, polyvinyl butyral adhesives, ethylene-vinyl acetate adhesives, and the like. By using a resin to which 0.1 to 30% by weight of a pigment is added, optically by bonding transparent resin plates, resin plates and resin films, resin plates and glass, resin films, resin films and glass, and glasses. Make a filter. In addition, when kneading and mixing by each method, additives such as an ultraviolet absorber and a plasticizer may be added.

  The near-infrared cut filter obtained by the present invention is used not only for imaging device applications and front plates of displays, but also for filter films that need to cut near-infrared rays, such as heat insulation films, optical products, sunglasses, etc. I can do it.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

[Synthesis Example 1] (Synthesis of 5-bromo-2,3,3-trimethyl-3H-indole)
To a 100 ml four-necked flask, 70 g of ethanol, 5.8 g of isopropyl methyl ketone, 10 g of 5-bromophenylhydrazine hydrochloride and 12.8 g of p-toluenesulfonic acid monohydrate were added, and the mixture was stirred at reflux temperature for 5 hours. did. After completion of the heating, the reaction solution is cooled to room temperature, water and ethyl acetate are added, and the mixture is separated, and the solvent of the organic layer is distilled off under reduced pressure to give 5-bromo-2,3,3-trimethyl-3H-indole. 9.2 g was obtained.

[Synthesis Example 2] (Synthesis of 5- (3,5-difluorophenyl) -2,3,3-trimethyl-3H-indole)
In a 200 ml four-necked flask, 9 g of 5-bromo-2,3,3-trimethyl-3H-indole, 7.6 g of 3,5-difluorophenylboronic acid, 16 g of tripotassium phosphate, tetrakis (triphenylphosphine) ) 0.87 g of palladium (0), 50 ml of toluene, 15 ml of isopropyl alcohol and 10 ml of pure water were added, and the mixture was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, water and toluene were added, liquid separation was performed, and the solvent of the organic layer was distilled off under reduced pressure. The obtained oily residue was purified by silica gel column chromatography (developing solution: chloroform) to obtain 6.5 g of 5- (3,5-difluorophenyl) -2,3,3-trimethyl-3H-indole.

[Synthesis Example 3] (Synthesis of 5- (3,5-difluorophenyl) -1-ethyl-2,3,3-trimethyl-3H-indolenin iodine salt)
To a 100 ml four-necked flask was added 20 ml of acetonitrile, 6 g of 5- (3,5-difluorophenyl) -2,3,3-trimethyl-3H-indole prepared in Synthesis Example 2 and 10 ml of iodoethane, and the mixture was refluxed. Stir for 3 hours. After completion of the heating, the reaction solution is cooled to room temperature, the precipitated solid is collected by filtration, washed with acetone and dried, and 5- (3,5-difluorophenyl) -1-ethyl-2,3,3-trimethyl- 7.5 g of 3H-indolenin iodine salt was obtained.

[Synthesis Example 4] (Synthesis of N-phenyl-2-phenyl-3-[(phenylamino) methylene] -1-cyclohexene-1-methanimine hydrochloride)
To a 500 ml four-necked flask, 15.6 g of 4-phenyl-1-cyclohexene and 110 g of N, N-dimethylformamide were added, and 73.3 g of phosphoryl chloride was slowly added dropwise under ice cooling. After completion of dropping, the reaction solution was heated to 95 ° C. and stirred for 4 hours. After completion of the heating, the reaction solution was cooled to room temperature, poured into 700 g of ice water, 40 g of aniline and 100 ml of concentrated hydrochloric acid were added with stirring, and the mixture was stirred at room temperature overnight. The precipitated solid was collected by filtration and purified by reprecipitation with ethyl acetate and hexane, and 15 N-phenyl-2-phenyl-3-[(phenylamino) methylene] -1-cyclohexene-1-methanimine hydrochloride was obtained. .5 g was obtained.

Example 1 (Synthesis of Compound 19 of the Present Invention)
In a 100 ml four-necked flask, 1.5 g of 5- (3,5-difluorophenyl) -1-ethyl-2,3,3-trimethyl-3H-indolenin iodine salt, N-phenyl-2-phenyl-3 -[(Phenylamino) methylene] -1-cyclohexene-1-methanimine hydrochloride 0.7 g, potassium tristrifluoromethanesulfonylmethide 1.2 g, sodium acetate 0.6 g, acetic acid 10 ml, acetic anhydride 10 ml was added and stirred at 100 ° C. for 3 hours. The reaction solution was cooled to room temperature, 150 ml of pure water was added to the reaction solution, and the precipitated solid was collected by filtration. This solid was purified by silica gel column chromatography (developing solution: chloroform) to obtain 0.5 g of compound 19 of the present invention.
Mass spectrum M ⁺ = 777, maximum absorption wavelength 780 nm (acetonitrile)

Example 2 (Synthesis of Compound 23 of the Present Invention)
In a 100 ml four-necked flask, 2 g of 5- (3,5-difluorophenyl) -1-ethyl-2,3,3-trimethyl-3H-indolenin iodine salt, 2-chloro-1-formyl-3- ( Hydroxymethylene) -1-cyclohexene (0.4 g), tristrifluoromethanesulfonylmethide potassium salt (1.6 g), acetic acid (10 ml) and acetic anhydride (10 ml) were added, and the mixture was stirred at 55 ° C. for 5 hours. The reaction solution was cooled to room temperature, 100 ml of pure water was added to the reaction solution, and the precipitated solid was collected by filtration. This solid was purified by silica gel column chromatography (developing solution: chloroform) to obtain 0.3 g of Compound 23 of the present invention.
Mass spectrum M ⁺ = 736, maximum absorption wavelength 802 nm (acetonitrile)

[Synthesis Example 5] (Synthesis of epoxy resin curing agent based on JP2014-80857)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 204 g of methyl ethyl ketone (hereinafter referred to as MEK), 294 g of tricyclodecane dimethanol, and 4-methylcyclohexane-1,2-dicarboxylic anhydride while purging with nitrogen. 423 g (manufactured by Shin Nippon Rika Co., Ltd., Rikacid MH) and 99 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical) were added and the mixture was heated at 50 ° C. for 2 hours. After the reaction, the mixture was heated and stirred at 70 ° C. for 4 hours. An additional 145 g of MEK was added to the resulting solution to obtain 1166 g of MEK solution of an epoxy resin curing agent. The resulting solution was colorless and the concentration was 70% by weight.

[Example 3] (Compound 19 of the present invention, epoxy resin composition, and production of near-infrared cut filter)
A glass separable flask equipped with a stirrer and a thermometer, and a glycidyl methacrylate skeleton random polymer (manufactured by NOF Corporation, Marproof G-0150M, epoxy equivalent 310 g / eq., Weight average molecular weight 10,000) as an epoxy resin. 50.0 g and 100 g of propylene glycol monomethyl ether acetate were added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, 0.50 g of the compound 19 of the present invention was added as a near infrared absorbing dye, and 20 to 35 ° C. The thermosetting resin composition was obtained by stirring until uniform. This thermosetting resin composition is dropped onto a glass substrate placed on a spin coater, and the substrate surface is coated by rotating the substrate at 1000 rpm for 30 seconds, and then dried at 80 ° C. for 10 minutes to remove the solvent. And thermosetting at 190 ° C. for 40 minutes to obtain a near-infrared cut filter. The obtained near-infrared cut filter used a spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer UV-3150), and measured the absorbance in the range of 300 to 1100 nm at a sampling pitch of 1 nm. The absorbance was measured after the near-infrared cut filter was dried at 80 ° C. for 10 minutes, thermally cured at 190 ° C. for 40 minutes, and then allowed to stand at 210 ° C. for 10 minutes. The absorbance at the maximum absorption wavelength of the spectral waveform of the obtained near-infrared cut filter is shown in Table 1 below.

[Example 4] (Preparation of compound 23 of the present invention, epoxy resin composition, and near-infrared cut filter)
A near-infrared cut filter was prepared in the same manner as in Example 3 except that the compound 23 of the present invention was used instead of the compound 19 of the present invention, and the spectral waveform was measured. The results are shown in Table 1 below.

[Comparative Example 1] (Preparation of an existing dye represented by the following formula (12), an epoxy resin composition, and a near-infrared cut filter)
A near-infrared cut filter was prepared in the same manner as in Example 3 except that a compound of the following formula (12) (see JP 2008-88426 A, λmax in methanol: 781 nm) was used instead of the compound 19 of the present invention. And measurement of the spectral waveform. The results are shown in Table 1 below.

[Example 5] (Preparation of compound 19 of the present invention, epoxy resin composition, and near-infrared cut filter)
In a glass separable flask equipped with a stirrer and a thermometer, 50.0 parts of fluorene resin (manufactured by Osaka Gas Chemical Co., Ltd., OGSOL PG-100, epoxy equivalent 260 g / eq.) As epoxy resin, 67 parts of cyclohexanone The mixture was stirred and dissolved at 20 to 35 ° C. for 2 hours, and then 1.0 part of the compound 19 of the present invention and 48 parts of the epoxy resin curing agent obtained in Synthesis Example 5 were added as a near infrared absorbing dye. A thermosetting resin composition was obtained by stirring until uniform at ˜35 ° C. This thermosetting resin composition is dropped onto a glass substrate placed on a spin coater, and the substrate surface is coated by rotating the substrate at 1000 rpm for 30 seconds, and then dried at 80 ° C. for 10 minutes to remove the solvent. And thermosetting at 190 ° C. for 40 minutes to obtain a near-infrared cut filter. The obtained near-infrared cut filter measured the spectral waveform by the same method as in Example 3. The results are shown in Table 1 below.

Example 6 (Production of Compound 23 of the Invention, Epoxy Resin Composition, and Near-Infrared Cut Filter)
A near-infrared cut filter was prepared and the spectral waveform was measured in the same manner as in Example 5 except that the compound 23 of the present invention was used instead of the compound 19 of the present invention. The results are shown in Table 1 below.

[Comparative Example 2] (Preparation of Existing Dye and Epoxy Resin Composition Represented by Formula (12) and Near Infrared Cut Filter)
A near-infrared cut filter was prepared and the spectral waveform was measured in the same manner as in Example 3 except that the compound of formula (12) was used instead of the compound 19 of the present invention. The results are shown in Table 1 below.

<Short-term heat resistance comparison>
In the near infrared cut filters obtained in Examples 3 and 4 and Comparative Examples 1 and 2, the spectral waveforms after drying at 80 ° C. for 10 minutes, leaving at 190 ° C. for 40 minutes, and leaving at 210 ° C. for 10 minutes are compared. Thus, the short-term heat resistance was compared. First, using the same spectrophotometer as in Example 3, the near-infrared cut filters of Examples 3 and 4 and Comparative Examples 1 and 2 were dried at 80 ° C. for 10 minutes, left at 190 ° C. for 40 minutes, and then at 210 ° C. The spectral waveform after standing for 10 minutes was measured. The heat resistance was compared using the absorbance at the maximum absorption wavelength of the near-infrared cut filters of Examples 3 and 4 and Comparative Examples 1 and 2, after thermosetting the absorbance after drying at 80 ° C. for 10 minutes (190 ° C., 40 The residual ratio of absorbance after the short-term heat test (210 ° C., 10 minutes) with respect to the absorbance after thermosetting (190 ° C., 40 minutes) is expressed by the following formulas (i) and (ii): Based on the above, each was compared. The calculation results are shown in Table 2 below, which means that the higher the residual ratio, the better the short-term heat resistance.

(Remaining rate after heat curing (190 ° C., 40 minutes)) = (Absorbance after heat curing (190 ° C., 40 minutes)) / (Absorbance after drying for 10 minutes at 80 ° C.) (i)

(Remaining rate after short-term heat test (210 ° C., 10 minutes)) = (Absorbance after short-term heat test (210 ° C., 10 minutes)) / (Absorbance after heat curing (190 ° C., 40 minutes)) (ii)

  As is clear from the results in Table 2, in comparison with Comparative Examples 1 and 2, Examples 3, 4, 5, and 6 have a high residual ratio of the cyanine compound of the present invention after thermosetting and after a short-term heat test. Therefore, it can be said that the thermosetting resin composition containing the cyanine compound of the present invention represented by the formula (1) as a near infrared absorbing dye has excellent heat resistance in the production of a near infrared cut filter. .

  The thermosetting resin composition containing the near-infrared absorbing dye of the present invention can be easily formed as a resin solution by a method such as spin coating, has excellent processability, and further obtained a near-infrared cut filter ( The optical filter) is very useful as an optical filter for various applications, especially as a near-infrared cut filter for image sensors such as CCD and CMOS, because the near-infrared absorption performance is small and heat resistance is high even when a thermal load is applied. It is.

Claims (15)

A fluorophenyl group-substituted cyanine compound represented by the following formula (1):

(In the formula, R ₁ is each independently an alkoxyalkyl group of 1 to 5 alkyl or C1-5 atoms, n is an integer of 1 to 5, the linking group D represents the following formula (2) Or Y is a hydrogen atom, a chlorine atom, an acyloxy group, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, * indicates a bonding site, and X ⁻ is a tris. (Trifluoromethanesulfonyl) methide anion.)

N in Formula (1) is an integer of 1-3, The fluorophenyl group substituted cyanine compound of Claim 1 characterized by the above-mentioned. N in Formula (1) is 2, The fluorophenyl group substituted cyanine compound of Claim 1 or 2 characterized by the above-mentioned. Formula (1) is following formula (4), The fluorophenyl group substituted cyanine compound as described in any one of Claims 1 thru | or 3 characterized by the above-mentioned.

(In the formula, R ₁ , D and X ⁻ have the same meanings as in formula (1).) The fluorophenyl group-substituted cyanine compound according to any one of claims 1 to 4, wherein Y in the formula (2) is a chlorine atom, a methyl group, an acetoxy group, or a phenyl group. The fluorophenyl group-substituted cyanine compound according to any one of claims 1 to 5, wherein Y in the formula (3) is a hydrogen atom or a phenyl group. R ₁ in Formula (1) and Formula (4) is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, or The fluorophenyl group-substituted cyanine compound according to any one of claims 1 to 6, which is a methoxyethyl group. A thermosetting resin composition comprising at least one compound according to any one of claims 1 to 7 as a near-infrared absorbing dye. The thermosetting resin composition according to claim 8, comprising an epoxy resin as the thermosetting resin. The thermosetting resin composition according to claim 9, wherein the epoxy resin has a fluorene skeleton. The thermosetting resin composition according to claim 10, wherein the epoxy resin has a structure represented by the following formula (5).

(Wherein ring Z is independent fused polycyclic aromatic hydrocarbon ring containing a benzene ring, R ₄ and R ₅ independently represent a cyano group, a halogen atom, an alkyl group, selected from an aryl group, R ₆ Each independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 1, x is an integer of 0 to 4, y is an integer of 0 or more, and z is an integer of 1 or more.) The two-ring Z in Formula (5) is a benzene ring, The thermosetting resin composition of Claim 11 characterized by the above-mentioned. A cured product of the thermosetting resin composition according to any one of claims 1 to 12. The near-infrared cut filter obtained from the thermosetting resin composition as described in any one of Claims 1 thru | or 13. An image sensor comprising the near-infrared cut filter according to claim 14.