JP2016075720A - Thermosetting resin composition comprising near-infrared absorbing dye, and near-infrared cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which makes it possible to prepare a near-infrared cut filter with high heat resistance, and a near-infrared cut filter with high heat resistance prepared therewith, particularly a near-infrared cut filter for an imaging element such as CCD and CMOS.SOLUTION: The present invention provides a thermosetting resin composition composed of a near-infrared absorbing dye, an epoxy resin, an organic salt, and an epoxy resin curing agent.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition containing a near-infrared absorbing dye, and a near-infrared filter (optical filter) using these.

  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 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, this glass filter having near-infrared absorption ability is very expensive. Moreover, since it is glass, there exists a problem in workability, the freedom degree of the design of an optical characteristic is narrow, and the response | compatibility to a spherical surface is also complicated. Furthermore, there is a limit to reducing the thickness of the glass, and there are problems in securing space and reducing the weight when incorporated into an imaging optical system. Therefore, it has been desired to develop a resin incorporating near-infrared absorption performance for producing a new near-infrared cut filter that can be formed into a thin film or a spherical surface.

  Then, development which produces a near-infrared cut filter by coating the resin composition containing a near-infrared absorption pigment | dye on the image pick-up element surface or the filter base-material surface is performed. However, since the optical filter produced by this method has insufficient heat resistance, development of a filter with higher heat resistance has been strongly desired.

  In Patent Document 2, a metal oxide is added to improve the heat resistance of the near-infrared absorbing dye. However, in this Patent Document 2, since a thermoplastic resin having a glass transition temperature of −80 to 0 ° C. is used, it is strongly affected by heat and oxygen, and is a filter for an image sensor that requires high heat resistance. The heat resistance is considered to be insufficient. Therefore, development of a filter with higher heat resistance has been strongly desired.

  From such a background, development of a near-infrared cut filter having high workability and heat resistance and a resin composition for producing the same are strongly demanded.

JP 62-128943 A JP 2010-079142 A

  An object of this invention is to provide the near-infrared cut filter excellent in workability and heat resistance produced using a resin composition, especially a thermosetting resin composition, and it.

  As a result of intensive studies, the present inventors have solved the above-mentioned problems with a thermosetting resin composition and a near-infrared cut filter comprising a near-infrared absorbing dye, an organic salt, and a thermosetting resin. As a result, the present invention was completed.

（式（１）及び式（２）において、Ｒ_１はそれぞれ独立に置換基を有してもよい炭素数１〜５のアルキル基又は置換基を有してもよい炭素数１〜５のアルコキシアルキル基を示し、Ｒ_２はハロゲン原子、置換基を有してもよい炭素数１〜５のアルキル基、置換基を有してもよい炭素数１〜５のアルコキシ基又はニトロ基、ｐは０又は１の整数を示し、Ｄが下記式（３）または式（４）のいずれかであり、Ｘ⁻はトリス（トリフルオロメタンスルホニル）メチドアニオンまたはビス（トリフルオロメタンスルホニル）イミドアニオンである。）

（式（３）中、Ｙは水素原子、塩素原子、置換基を有してもよいフェニル基、置換基を有してもよい炭素数１〜６のアルキルアミノ基のいずれかであり、＊は結合部位を示す。）

（式（４）中、Ｙは水素原子、塩素原子、置換基を有してもよいフェニル基、置換基を有してもよい炭素数１〜６のアルキルアミノ基のいずれかであり、＊は結合部位を示す。）

（式（５）中、Ｒ_３はそれぞれ独立に置換基を有してもよい炭素数１〜７のアルキル基又は置換基を有してもよい炭素数１〜５のアルコキシアルキル基を示し、Ｘ⁻はトリス（トリフルオロメタンスルホニル）メチドアニオン又はビス（トリフルオロメタンスルホニル）イミドアニオンである。）
［４］有機塩（Ｂ）が、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオンまたはセシウムイオンから選ばれる金属イオン、または窒素オニウムイオン、リンオニウムイオンまたは硫黄オニウムイオンから選ばれるオニウムイオンと、メチルベンゼンスルホネート（ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻）、カルボキシベンゼンスルホネート（ＣＯＯＨ（Ｃ_６Ｈ_４）ＳＯ_３ ⁻）、ベンゾエート（Ｃ_６Ｈ_５ＣＯＯ⁻）、トリフルオロアセテート（ＣＦ_３ＣＯＯ⁻）、トリフルオロメタンスルホネート（ＣＦ_３ＳＯ_２ ⁻）、テトラベンジルボレート（Ｂ（Ｃ_６Ｈ_５）_４ ⁻）、ビス（トリフルオロメタンスルホニル）イミドアニオンのいずれかより選ばれるアニオンからなることを特徴とする［１］乃至［３］のいずれか一つに記載の熱硬化性樹脂組成物、
［５］有機塩（Ｂ）が、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオンより選ばれる金属イオンと、ビス（トリフルオロメタンスルホニル）イミドアニオンからなることを特徴とする［１］乃至［４］のいずれか一つに記載の熱硬化性樹脂組成物、
［６］エポキシ樹脂（Ｃ）のエポキシ当量が１５０〜６００ｇ／ｅｑ.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熱硬化性樹脂組成物、
［７］エポキシ樹脂（Ｃ）がメタクリル酸グリシジル骨格のみで構成された重合体、あるいはメタクリル酸グリシジル骨格を主としてアクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、ビニル置換芳香族化合物のいずれかの組み合わせで構成される共重合体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熱硬化性樹脂組成物、
［８］エポキシ樹脂（Ｃ）がフルオレン骨格を有するエポキシ化合物であることを特徴とする［１］乃至［７］のいずれか一つに記載の熱硬化性樹脂組成物、
［９］近赤外線吸収色素（Ａ）が、下記式（６）または式（７）で表されるシアニン化合物のいずれかを少なくとも１種を含むことを特徴とする［１］乃至［８］のいずれか一つに記載の熱硬化性樹脂組成物、

（式（６）及び式（７）において、Ｒ_４はそれぞれ独立にメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基、メトキシエチル基、ｎ−ブトキシエチル基、Ｙは水素原子又は塩素原子、Ｘ⁻はトリス（トリフルオロメタンスルホニル）メチドアニオン又はビス（トリフルオロメタンスルホニル）イミドアニオンである。）
［１０］［１］乃至［９］のいずれか一つに記載の熱硬化性樹脂組成物の硬化物、
［１１］［１］乃至［１０］のいずれか一つに記載の熱硬化性樹脂組成物を用いて成形した近赤外線カットフィルタ、
［１２］［１１］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 near-infrared absorbing dye (A), an organic salt (B) composed of an anion other than a tris (trifluoromethanesulfonyl) methide anion and a cation of a metal ion or an onium ion, and an epoxy resin (C) A thermosetting resin composition,
[2] The thermosetting resin composition according to [1], wherein the near-infrared absorbing dye (A) contains at least one of a cyanine compound or a diimonium compound,
[3] The near-infrared absorbing dye (A) contains at least one of a cyanine compound represented by the following formula (1) or formula (2) and a diimonium compound represented by the following formula (5). The thermosetting resin composition according to [1] or [2],

(In the formula (1) and the formula (2), R ₁ each independently of carbon atoms 1 to 5 an optionally substituted alkyl group or an alkoxy having 1 to 5 carbon atoms which may have a substituent R ₂ represents a halogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms or a nitro group, p is Represents an integer of 0 or 1, D is either the following formula (3) or formula (4), and X ⁻ represents a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion.

(In Formula (3), Y is any one of a hydrogen atom, a chlorine atom, an optionally substituted phenyl group, and an optionally substituted alkylamino group having 1 to 6 carbon atoms, * Indicates a binding site.)

(In Formula (4), Y is any one of a hydrogen atom, a chlorine atom, an optionally substituted phenyl group, and an optionally substituted alkylamino group having 1 to 6 carbon atoms, * Indicates a binding site.)

(In Formula (5), each R ₃ independently represents a C 1-7 alkyl group which may have a substituent or a C 1-5 alkoxyalkyl group which may have a substituent, X ⁻ is a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion.
[4] An organic salt (B) is a metal ion selected from lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion, or an onium ion selected from nitrogen onium ion, phosphorus onium ion or sulfur onium ion, and methyl Benzene sulfonate (CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ ), carboxybenzene sulfonate (COOH (C ₆ H ₄ ) SO ₃ ⁻ ), benzoate (C ₆ H ₅ COO ⁻ ), trifluoroacetate (CF ₃ COO ⁻⁾ ), Trifluoromethanesulfonate (CF ₃ SO ₂ ⁻ ), tetrabenzyl borate (B (C ₆ H ₅ ) ₄ ⁻ ), or an anion selected from bis (trifluoromethanesulfonyl) imide anions. [1] to [ The thermosetting resin composition according to any one of,
[5] The organic salt (B) comprises a metal ion selected from lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion, and a bis (trifluoromethanesulfonyl) imide anion. [4] The thermosetting resin composition according to any one of
[6] The thermosetting resin composition according to any one of [1] to [5], wherein an epoxy equivalent of the epoxy resin (C) is 150 to 600 g / eq.
[7] A polymer in which the epoxy resin (C) is composed only of a glycidyl methacrylate skeleton, or a glycidyl methacrylate skeleton mainly consisting of acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, or a vinyl-substituted aromatic compound The thermosetting resin composition according to any one of [1] to [6], which is a copolymer composed of a combination of
[8] The thermosetting resin composition according to any one of [1] to [7], wherein the epoxy resin (C) is an epoxy compound having a fluorene skeleton,
[9] The near-infrared absorbing dye (A) contains at least one cyanine compound represented by the following formula (6) or formula (7): The thermosetting resin composition according to any one of the above,

(In the formulas (6) and (7), R ₄ each independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxy group, An ethyl group, an n-butoxyethyl group, Y is a hydrogen atom or a chlorine atom, and X ⁻ is a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion.)
[10] A cured product of the thermosetting resin composition according to any one of [1] to [9],
[11] A near-infrared cut filter formed using the thermosetting resin composition according to any one of [1] to [10],
[12] An image sensor provided with the near infrared cut filter according to [11],
About.

  According to the present invention, a near-infrared cut filter having high heat resistance, in particular, a near-infrared cut filter for an image sensor such as a CCD or CMOS, and a thermosetting resin composition capable of producing them can be provided. However, the use of the thermosetting resin composition of the present invention is not limited to these.

  The present invention relates to a thermosetting resin composition comprising a near-infrared absorbing dye (A), an organic salt (B) having a metal ion or an onium ion, and an epoxy resin (C).

  The near-infrared absorbing dye (A) used in the present invention is not particularly limited as long as it is a dye having an absorption peak in the near-infrared region (700 to 2000 nm). Examples of the dye compound used in the present invention include a cyanine compound, a phthalocyanine compound, an azo compound, a diimonium compound, a squarylium compound, a Ni dithiol compound, a Cu complex compound, a croconium compound, an anthraquinone compound, and a pyromethene compound, and among them, a cyanine compound or a diimonium compound. Are preferably used.

  The near-infrared absorbing dye (A) used in the present invention is selected from either a cyanine compound represented by the following formula (1) or formula (2) or a diimonium compound represented by the following formula (5). . Each dye compound will be described in detail below.

The cyanine compound used in the present invention is represented by the above formula (1) or formula (2), and R ₁ in both formulas each independently has an optionally substituted alkyl group having 1 to 5 carbon atoms or A C 1-5 alkoxyalkyl group which may have a substituent, R ₂ may have a halogen atom, a C 1-5 alkyl group which may have a substituent, or a substituent. A good C1-C5 alkoxy group or nitro group is represented. p is an integer of 0 or 1, and 0 is preferable.

In R ₁ and R ₂ of Formula (1) and Formula (2), 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, and iso. -Propyl group, 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, etc. It is done.

In R ₁ and R ₂ of formula (1) and formula (2), the alkoxyalkyl group having 1 to 5 carbon atoms is not particularly limited, but is a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, Propoxyethyl group, n-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group Etc.

In R ₁ and R ₂ of Formula (1) and Formula (2), the substituent that the alkyl group having 1 to 5 carbon atoms may have is not particularly limited, but examples thereof include an alkoxy group, An alkoxyalkyl group in which hydrogen of the alkyl group is substituted with an alkoxy group, an alkoxyalkoxyalkyl group substituted with an alkoxyalkoxy group, an alkoxyalkoxyalkoxyalkyl group substituted with an alkoxyalkoxyalkoxy group, etc .; a substituted or unsubstituted amino group ( Alkylalkyl group and dialkylaminoalkyl group), alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, halongen 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 and R ₂ are preferably a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, and an n-butoxyethyl group, and particularly preferably a methoxyethyl group.

In R ₁ and R ₂ of formula (1) and formula (2), the substituent that the alkoxyalkyl group having 1 to 5 carbon atoms may have is not particularly limited. An alkoxy group, an alkoxyalkoxyalkoxy group, and the like; a halogenon atom, a substituted or unsubstituted amino group (dialkylamino group and the like), an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkoxysulfonyl group, and the like.

In R ₂ of formula (1) and formula (2), the halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The bonding group D in the formulas (1) and (2) is represented by the following formula (3) or (4), and * represents a binding site. Y in Formula (3) and Formula (4) is a hydrogen atom, a chlorine atom, a phenyl group, an optionally substituted phenyl group, or an optionally substituted alkylamino group having 1 to 6 carbon atoms. Either is a chlorine atom.

  When Y in the above formulas (3) and (4) is a phenyl group, the phenyl group may have a substituent, and the substituent is not particularly limited. For example, a methyl group, an ethyl group, n -Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, methoxymethyl group, methoxyethyl Group, ethoxyethyl group, propoxyethyl group, methoxy group, ethoxy group, n-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethi Xymethyl group, dimethoxyethyl group, diethoxyethyl group, n-propoxy group, iso-propoxy group, n-butoxy group, iso Butoxy, sec- butoxy, t-butoxy group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In Y in the above formulas (3) and (4), the alkylamino group having 1 to 6 carbon atoms is not particularly limited, but a secondary alkylamino group having 1 to 6 carbon atoms is preferable. For example, dimethylamino group, diethylamino group, diisopropylamino group, pyrrolidine, and piperidine are preferable.

  In Y in the above formula (3) and formula (4), the substituent that the alkylamino group having 1 to 6 carbon atoms may have is not particularly limited, but an alkoxy group, an alkoxyalkoxy group, Examples include an alkoxyalkoxyalkoxy group, a halogenon atom, a substituted or unsubstituted amino group (such as a dialkylamino group), an alkoxycarbonyl group, an alkylaminocarbonyl group, and an alkoxysulfonyl group.

  Of the above formulas (1) and (2), a cyanine compound represented by formula (1) is preferred, and more specifically, formula (1) is represented by the following formula (6) or formula (7), Formula (7) is used suitably for the near-infrared cut off filter of this invention from a heat resistant and transparent viewpoint.

In the above formulas (6) and (7), R ₄ is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, methoxyethyl group. , N-butoxyethyl group, methoxyethyl group is preferred.

  In the above formulas (6) and (7), Y is selected from a hydrogen atom or a chlorine atom, and a chlorine atom is preferred.

In R ₃ of the above formula (5), the alkyl group having 1 to 7 carbon atoms is not particularly limited, but any of a normal butyl group, an isobutyl group, a secondary butyl group, a methoxyethyl group, and a cyanopropyl group More preferred are a normal butyl group and an isobutyl group, and even more preferred is an isobutyl group. The optical isomer of the secondary butyl group is not particularly limited.

In R ₃ of the above formula (5), the alkoxyalkyl group having 1 to 5 carbon atoms is not particularly limited, but is a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, n-butoxy. Examples include ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group, etc. A methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, and an n-butoxyethyl group are preferable, and a methoxyethyl group is particularly preferable.

In R ₃ of the above formula (5), the substituent that the alkyl group having 1 to 7 carbon atoms and the alkoxyalkyl group having 1 to 5 carbon atoms may have is not particularly limited, but an alkoxy group An alkoxyalkoxy group, an alkoxyalkoxyalkoxy group, and the like; a halogenon atom, a substituted or unsubstituted amino group (such as a dialkylamino group), an alkoxycarbonyl group, an alkylaminocarbonyl group, and an alkoxysulfonyl group.

Further, when the near-infrared absorbing dye (A) is a cationic dye, the counter anion is not particularly limited, but from the viewpoint of heat resistance and transparency of the cured product (near-infrared cut filter of the present invention), the above formula ( 1), the formula (2), the formula (5), the formula (6), and the formula (7) have X ⁻ is a tris (perhalogenoalkylsulfonyl) imide anion represented by the following formula (8), or the following formula ( The tris (perhalogenoalkylsulfonyl) methide anion represented by 9) is preferable, and the tris (perhalogenoalkylsulfonyl) methide anion is more preferable. Furthermore, in the present invention, a tris (trifluoromethylsulfonyl) methide anion in which n is 1 and Q is fluorine in the following formula (9) is particularly preferable.

（式（８）中、ｎは１〜５、Ｑはフッ素、塩素、臭素若しくはヨウ素を示す。）

(In formula (8), n represents 1 to 5, and Q represents fluorine, chlorine, bromine or iodine.)

（式（９）中、ｎは１〜５、Ｑはフッ素、塩素、臭素またはヨウ素を示す。）

(In formula (9), n represents 1 to 5, Q represents fluorine, chlorine, bromine or iodine.)

  When the near-infrared absorbing dye (A) contained in the near-infrared cut filter of the present invention does not dissolve in the thermosetting resin composition of the present invention, it is used by mixing and dispersing with other components while making the insoluble dye fine particles. can do.

  Examples of the method of mixing and dispersing include known methods such as a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, and the like. Among these, a sand mill (bead mill) is preferable. Further, in the pulverization of the pigment particles in the sand mill (bead mill), it is preferable to use a bead having a small diameter and to perform the treatment under the condition of increasing the pulverization efficiency by increasing the filling rate of the beads. Furthermore, it is preferable to remove beads and coarse particles used for dispersion by filtration, centrifugation, or the like after the pulverization treatment.

Examples of the anion of the organic salt used in the present invention (B), is not particularly limited, for example, methyl benzene sulfonate _{(CH 3 (C 6 H 4} ) SO 3 -), carboxymethyl sulfonate _(COOH (C _{6 H} 4) SO ₃ ^-), benzoate ^{_{(C 6 H 5 COO -)}} , trifluoroacetate _(CF 3 COO ^-), trifluoromethanesulfonate _(CF 3 SO ₂ ^-), tetra benzyl borate _{(B (C 6 H 5)} 4 -) And bis (trifluoromethanesulfonyl) imide anion, and the like. From the viewpoint of heat resistance and transparency, bis (trifluoromethylsulfonyl) imide anion is preferable.

  Although it does not restrict | limit especially as a cation of the organic salt (B) used for this invention, It is either a metal ion or an onium ion, For example, metals, such as a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a cesium ion An ion; an onium ion such as a nitrogen onium ion, a phosphorus onium ion, or a sulfur onium ion, preferably a potassium ion or a cesium ion, and a potassium ion is particularly preferable from the viewpoint of heat resistance and transparency.

  The addition amount of the organic salt (B) is not particularly limited, but is usually 0.001% by weight to 100% by weight with respect to the epoxy resin (C) to be used. From the viewpoint of heat resistance, it is preferable that the addition amount of the organic salt (B) is larger than that of the epoxy resin (C), but the addition amount is limited from the viewpoint of compatibility with the epoxy resin (C). Therefore, from the balance of both, the addition amount of the organic salt (B) to the epoxy resin (C) is preferably 0.01% by weight to 50% by weight, more preferably 0.1% by weight to 30% by weight, and 1.0% % By weight to 10% by weight is more preferable, and 3.0% by weight to 10% by weight is particularly preferable.

  Examples of the epoxy resin (C) include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group Examples thereof include copolymers with other polymerizable unsaturated compounds. In addition, an epoxy resin having a fluorene skeleton such as a 9,9-bisarylfluorene skeleton can be given.

  Examples of the epoxy resin that is a glycidyl etherified product of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3 -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, 2,2′-methylene- Bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglicinol, diisopropyl Examples thereof include phenols having a redene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of the epoxy resin that is a glycidyl etherified product of the above-mentioned various novolak resins include, for example, phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and naphthols Examples include novolak resins made from phenol, phenol novolak resins containing xylylene skeletons, phenol novolac resins containing dicyclopentadiene skeletons, phenol novolac resins containing biphenyl skeletons, phenol novolac resins containing fluorene skeletons, and the like. .

Examples of the alicyclic epoxy resin include fats having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. Examples thereof include cyclic epoxy resins.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.

  Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

  Examples of the glycidyl ester epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.

  Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.

  Examples of the epoxy resin obtained by glycidylation of the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A. And epoxy resins obtained by glycidylation of halogenated phenols such as

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, Marproof G-0115S, G-0130S, and G-0250S are commercially available products. G-1010S, G-1005S, G-0150M, G-2050M (manufactured by NOF Corporation), and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, Examples thereof include glycidyl methacrylate and 4-vinyl-1-cyclohexene-1,2-epoxide. 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.

The epoxy equivalent of the epoxy resin (C) used in the present invention is preferably 100 to 2500 g / eq., More preferably 100 to 1500, still more preferably 150 to 600, and particularly preferably 280 to 350.

  The weight average molecular weight of the epoxy resin (C) used in the present invention is preferably 5,000 to 250,000, more preferably 5,000 to 20,000, and further preferably 5,000 to 10,000. The epoxy resin (C) may be used alone or in combination of two or more.

Examples of the epoxy resin having a fluorene skeleton include the following formula (10). Ring Z in formula (10) is a condensed polycyclic aromatic hydrocarbon ring containing an independent benzene ring, R ₅ and R ₆ are each an independent substituent, and R ₇ is each independently a hydrogen atom or methyl. X represents an integer of 0 to 4, y is an integer of 0 or more, and z is an integer of 1 or more.

  In the above formula (10), the condensed polycyclic aromatic hydrocarbon ring represented by the ring Z is a condensed bicyclic hydrocarbon ring (for example, a condensed bicyclic hydrocarbon ring having 8 to 20 carbon atoms such as an indene ring or a naphthalene ring). Condensed bicyclic to tetracyclic hydrocarbon rings such as cyclic hydrocarbon rings (preferably C10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (eg anthracene ring, phenanthrene ring, etc.) Etc. 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 preferable, and a benzene ring is most preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and may usually be 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 a 2-naphthyl group is especially preferable.

Examples of the substituent represented by R ₅ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, an aryl group (having 6 to 6 carbon atoms such as a phenyl group). Non-reactive substituents such as 10 aryl groups) and the like, and in particular, a halogen atom, a cyano group or an alkyl group in many cases. Examples of the alkyl group include a C1-C6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C1-C4 alkyl group, particularly a methyl group). It can be illustrated. When x is plural (2 or more), R ₅ may be different from each other or the same. Further, R ₅ substituted on two benzene rings constituting the fluorene skeleton may be the same or different. Further, the bonding position (substitution position) of R ₅ to the benzene ring constituting the fluorene skeleton is not particularly limited. The preferred substitution number x is 0 or 1, with 0 being particularly preferred. In the two benzene rings constituting the fluorene skeleton, the number of substitutions x may be the same or different from each other.

Examples of the substituent R ₆ substituted on the ring Z include 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, and a butyl group, preferably 1 to 1 carbon atoms). An alkyl group having 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group (a cycloalkyl group having 5 to 8 carbon atoms such as a cyclohexyl group), preferably a cycloalkyl group having 5 to 6 carbon atoms. Etc.), aryl groups (for example, aryl groups having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, preferably aryl groups having 6 to 10 carbon atoms, more preferably aryl groups having 6 to 8 carbon atoms) ), Hydrocarbon groups such as aralkyl groups (C6-C10 aryl-substituted C1-C4 alkyl groups such as benzyl and phenethyl groups); alkoxy groups (meth) An alkoxy group having 1 to 8 carbon atoms such as a xyl 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 (6 carbon atoms). group -OR ₈ [wherein such an aryloxy group) of to 10, _{R 8} is a hydrocarbon group (synonymous to hydrocarbon groups of the.) shows a. An alkylthio group (an alkylthio group having 1 to 8 carbon atoms such as a methylthio group, preferably an alkylthio group having 1 to 6 carbon atoms) or the like —SR ₈ (in the formula, synonymous with R ₈ ); acyl A group (such as an acyl group having 1 to 6 carbon atoms such as an acetyl group); an alkoxycarbonyl group (such as an alkoxycarbonyl group having 1 to 4 carbon atoms such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Hydroxyl group; nitro group; cyano group; substituted amino group (for example, dialkylamino group such as dimethylamino group) and the like.

Among these, R ₆ 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. R ₆ is preferably a hydrocarbon group (for example, an alkyl group having 1 to 6 carbon atoms), an alkoxy group (such as an alkoxy group having 1 to 4 carbon atoms), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Etc.).

In the same ring Z, when y is plural (2 or more), R ₆ may be different from each other or the same. In the two rings Z, R ₆ may be the same or different. Moreover, 0-8 are preferable, as for the substitution number y, 0-6 are more preferable, 0-4 are more preferable, and 0-2 are especially preferable. In the two rings Z, m may be the same or different from each other.

The substituent R ₇ is a hydrogen atom or a methyl group, and preferably a hydrogen atom.

  z should just be one or more, for example, 1-4, Preferably it is 1-3, More preferably, it is 1-2, More preferably, it is 1. In addition, z may be the same or different in each ring Z and is usually the same in many cases. The substitution position of the epoxy group-containing group is not particularly limited as long as it is substituted at an appropriate substitution position of ring Z.

  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. , 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 preferable.

  Examples of the compound represented by the formula (10) include 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis ( 3-glycidyloxyphenyl) fluorene, etc.], 9,9-bis (glycidyloxynaphthyl) fluorene [eg, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5-glycidyl) A compound in which z is 1 in the above formula (10), such as oxy-1-naphthyl) fluorene and the like.

  The epoxy equivalent of the epoxy resin 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. . Examples of products available from the market include Oxol series (Osaka Gas Chemical Co., Ltd.) such as Ogsol PG-100 and CG-500.

  The thermosetting resin composition of the present invention comprises an epoxy resin (C) represented by the above epoxy resin (a polymerizable unsaturated compound having an epoxy group represented by the Marproof series and other other resins). A copolymer with a polymerizable unsaturated compound and / or an epoxy compound having a fluorene skeleton typified by the ogsol series) may be used alone, as long as the effect of the present invention is not impaired. An epoxy resin may be included. Other epoxy resins include glycidyl ether type epoxy resins, such as bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, 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 (such as triphenolmethane type epoxy resin), phenol aralkyl type epoxy resin, heterocyclic type epoxy resin (epoxy resin containing xanthene unit) ), Stilbene type epoxy resins, condensed ring aromatic hydrocarbon modified epoxy resins (1,6-bis (glycidyloxy) naphthalene, bis (2,7-bis (glycidyloxy)) ) Naphthalene ring-containing epoxy resins such as naphthalene) alkanes), glycidyl ester type epoxy resins, other epoxy resins having a fluorene skeleton. You may use these other epoxy resins individually or in combination of 2 or more types.

  When other epoxy resins are used, a copolymer of a polymerizable unsaturated compound having an epoxy group represented by the Marproof series and other polymerizable unsaturated compounds, with respect to the entire epoxy resin component, and / or Or the ratio of the epoxy resin which has a fluorene skeleton represented by the ogsol series is 50 to 99.5 weight% normally, 70 to 97 weight% is preferable and 90 to 98 weight% is further more preferable.

  In this invention, the epoxy resin hardening | curing agent for hardening an epoxy resin (C) can be added as needed. Examples of the epoxy resin curing agent used include acid anhydride compounds and polyvalent carboxylic acids, and examples of curing agents that can be used in combination include amine compounds, amide compounds, and phenol compounds. When these curing agents are added, a polyvalent carboxylic acid is preferable from the viewpoint of heat resistance and transparency of a cured product (such as the near-infrared cut filter of the present invention), and has two or more carboxylic anhydride groups in the molecule. Compounds are particularly preferred.

  Examples of the acid anhydride compound 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, and the like. . Among them, from the viewpoint of light resistance, transparency, and workability, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 2,4-diethyl glutaric anhydride, Butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1, 3,4-tricarboxylic acid-3,4-anhydride and the like are preferable.

  The polyvalent carboxylic acid having two or more carboxyl groups is preferably a bifunctional or higher functional carboxylic acid, and is not particularly limited even when a geometric isomer or optical isomer is present. For example, 1,2,3,4 -Butanetetracarboxylic acid, 1,2,3, -propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, alkyltricarboxylic acids such as citric acid; phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydro Aliphatic cyclic polycarboxylic acids such as phthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid and methylnadic acid; multimers of unsaturated fatty acids such as linolenic acid and oleic acid and dimer acids which are reduced products thereof Malic acid; butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonane Acid, linear alkyl diacids of decanedioic acid; bicyclo [2,2,1] heptane-2,3-dicarboxylic acid, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid, cyclohexane-1 , 3,4-tricarboxylic acid, polyvalent carboxylic acid having a bicyclo structure such as octahydro-1H-4,7-methanoindene-2,5-dicarboxylic acid, and the like.

  Moreover, in this invention, the polyhydric carboxylic acid obtained by making it react with the polyhydric carboxylic acid anhydride or polyhydric carboxylic acid which has alcohol more than bifunctional commercially available can also be used. Examples of the polyvalent carboxylic acid anhydride or polyvalent carboxylic acid include the above-mentioned compounds, and the alcohols are not particularly limited in geometric isomers or optical isomers, and include ethylene glycol, 1,3-propanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,5-hexanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A alkylene oxide adduct, bisphenol S In addition to alkylene oxide adducts, 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, adamantanetriol, octahydro-1H-4,7-methanoindenediol, octahydro- Examples thereof include aliphatic alcohols having 2 to 30 carbon atoms such as 1H-4,7-methanoindenyldimethanol.

  In the thermosetting resin composition of the present invention, the epoxy resin curing agent may be used alone or in combination of two or more. As a usage-amount, the ratio of 0.01-150 weight% is preferable with respect to an epoxy resin (C), the ratio of 1-100 weight% is more preferable, the ratio of 30-80 weight% is further more preferable, 40-70 A percentage by weight is particularly preferred.

  As the epoxy resin curing agent used in the present invention, even when a curing agent other than the above-mentioned acid anhydride and / or polyvalent carboxylic acid is used in combination, the total amount of the acid anhydride and / or polyvalent carboxylic acid is the total curing agent. The proportion of the content is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  Examples of the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like. Specific examples of curing agents that can be used include amines (1,4-butanediamine) and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine. Polyamide resins synthesized), polyhydric phenols (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, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis ( 4- Hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, 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 ' Polycondensates with bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, Examples include, but are not limited to, condensates of pens and phenols, and others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc.) These may be used alone or in combination The above may be used.

  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-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent. These coupling agents may be used alone or in combination of two or more. A coupling agent is 0.05-20 weight part normally in the thermosetting resin composition of this invention, Preferably 0.1-10 weight part is contained as needed.

  In the thermosetting resin composition of the present invention, it is possible to supplement mechanical strength without impairing transparency by using a nano-order level inorganic filler as required. The average particle size of the inorganic filler used is 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. The content of these inorganic fillers is suitably used in the range of 0 to 95% by weight with respect to the total amount of the thermosetting resin composition of the present invention.

  In order to prevent coloration, an amine compound as a light stabilizer, or a phosphorus compound and a phenol compound as an antioxidant can be added to the thermosetting resin composition of the present invention.

  Examples of the amine compound as the light stabilizer 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- Mixed esterified product of decanedioic acid with pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2, , 6, -tetramethyl-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-hydroxyl Nyl] methyl] butyl malonate, 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) -triazine -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-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl Amino-1, 3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]], 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- Tet Lamethyl-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, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetra Hindered amines such as methyl-4-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) -Tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Reaction product of -di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- Benzotria such as (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol Compounds, benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5- Triazine compounds such as triazin-2-yl) -5-[(hexyl) oxy] phenol and the like are mentioned, and hindered amine compounds are particularly preferable.

  A commercial item can be used for the said amine compound. The commercially available amine compound is not particularly limited, and for example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA- 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus-based compound as the antioxidant is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl penta Erythritol diphosphite, 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-Buchi Phenyl) 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-butyl) Enyl) -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 , Triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate And the like.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, the product made from ADEKA, 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 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP and the like.

  The phenol compound as the antioxidant 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-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1 , 6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanur Late, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl Benzene, pentaerythrityl-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-butylphenol), 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-butyl) Ruphenol), 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 the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , 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, Sumitizer GA-80 , Sumilizer MDP-S, Sumili zer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. are mentioned.

  In addition, an additive marketed as an anti-coloring agent for epoxy resin can be used. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the above amine compounds, phosphorus compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is based on the total weight of the thermosetting resin composition of the present invention. And preferably used in the range of 0.005 to 5.0% by weight.

  The near-infrared cut filter (optical filter) using the thermosetting resin composition of the present invention may be provided on a base material or the base material itself. The substrate is not particularly limited as long as it can be generally used for an optical filter, but a substrate made of glass or resin is usually used. The thickness of the layer is usually about 0.05 μm to 10 mm, but can be 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 / Tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer such as vinyl acetate copolymer or fluorine compound copolymer, 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.

  Although it does not specifically limit as a method of producing the infrared cut filter (optical filter) using the thermosetting resin composition of this invention, For example, the following well-known method can be utilized. 1) A near-infrared absorbing dye (A) and an organic salt (B) are dissolved in an epoxy resin (C) and a curing agent to form a thermosetting resin composition of the present invention, and after molding, heat cured to form a resin plate or film 2) A paint containing a near-infrared absorbing dye (A), an organic salt (B), and an epoxy resin (C) is prepared to obtain the thermosetting resin composition of the present invention, and a transparent resin plate, transparent A method of coating a film, a transparent glass plate, or an imaging device, 3) a method of sandwiching the thermosetting resin composition of the present invention with a substrate, and producing a laminated resin plate, a laminated resin film, or a laminated glass plate, etc. is there.

  In the method 1), a near-infrared absorbing dye (A) and an organic salt (B) are dissolved in an epoxy resin (C) and a curing agent, and injected into a mold to obtain a thermosetting resin composition of the present invention, and heated. Examples of the method include molding by reacting and curing, or pouring into a mold and heating reaction until a hard product is formed in the mold. Depending on the composition used, the processing temperature, filming (resin plate) conditions, etc. are somewhat different, but usually curing conditions at 100 to 200 ° C. for about 30 minutes to 5 hours are applied. The amount of the near-infrared absorbing dye added is appropriately determined according to the target near-infrared cut rate, and varies depending on the thickness, absorption strength, visible light transmittance, etc. of the resin plate or film to be produced. Is used in an amount of about 0.01 to 30% by weight, preferably about 0.01 to 15% by weight.

  The method 2) is a method in which a near-infrared absorbing dye (A) and an organic salt (B) are dissolved in an epoxy resin (C) to form a paint (thermosetting resin composition of the present invention). A thermosetting resin composition) can be used to use a solvent. 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 a near-infrared absorption pigment | dye (A) changes with the thickness of the coating to produce, absorption intensity, and visible light transmittance | permeability, it is about 0.01 to 30 weight% generally with respect to an epoxy resin (C). The coating material thus obtained is coated with a spin coater, bar coater, roll coater, gravure coater, offset coater, spray or the like on a transparent resin plate, a transparent film, a transparent glass plate, or an image pickup device. The near-infrared absorption cut filter or an image sensor provided with the same can be obtained.

  The near-infrared cut filter of the present invention for near-infrared absorption (hereinafter referred to as an optical filter) is not limited to the imaging device application or the front plate of the display, but a filter film that needs to cut near-infrared rays, for example, a heat insulating film, It can also be used for optical products and sunglasses.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Here, the part represents part by weight unless otherwise specified.

[Example 1]
In a glass separable flask equipped with a stirrer and a thermometer, epoxy resin (C) glycidyl methacrylate skeleton block copolymer Marproof G-0150M (manufactured by NOF Corporation, epoxy equivalent 310 g / eq.) 50.0 Then, 100 parts of cyclohexanone was added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, as a near-infrared absorbing dye (A), a compound of the following formula (12) (λmax in methanol: 781 nm, JP2008 -88426) was added and stirred at 20-35 ° C until uniform. Add 0.5 parts of bis (trifluoromethanesulfonyl) imide potassium (1.0% by weight with respect to Marproof G-0150M) as organic salt (B) and stir at 20-35 ° C. for 1 hour until uniform. A thermosetting resin composition of the present invention was obtained. 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 cured at 190 ° C. for 40 minutes to obtain an optical filter.
The obtained optical filter was dried at 80 ° C. for 10 minutes, heat-cured at 190 ° C. for 40 minutes, and allowed to stand at 210 ° C. for 10 minutes. The spectrophotometer (UV-visible spectrophotometer UV, manufactured by Shimadzu Corporation) -3150), a range of 300 to 2000 nm was measured at a sampling pitch of 1 nm.

[Example 2]
The organic salt (B) was mixed with 0.5 parts of bis (trifluoromethanesulfonyl) imide potassium described in Example 1 (1.0% by weight based on Marproof G-0150M) (1.5 parts of Marproof G-). An optical filter was prepared in the same manner as in Example 1 except that the content was changed to 3.0% by weight with respect to 0150M, and a spectral waveform was measured.

[Example 3]
The organic salt (B) was mixed with 0.5 parts of bis (trifluoromethanesulfonyl) imide potassium described in Example 1 (1.0% by weight based on Marproof G-0150M) (5.0 parts of Marproof G-). An optical filter was produced in the same manner as in Example 1 except that it was changed to 10.0% by weight with respect to 0150M, and a spectral waveform was measured.

[Comparative Example 1]
An optical filter for comparison was prepared in the same manner as in Example 1 except that bis (trifluoromethanesulfonyl) imide potassium was not added as the organic salt (B), and the spectral waveform was measured.

  Table 1 shows the measurement results of the absorbance at the maximum absorption wavelength of the spectral waveforms of the optical filters obtained in Examples 1 to 3 and Comparative Example 1.

[Short-term heat resistance comparison]
The optical filters obtained in Examples 1 to 3 and Comparative Example 1 were dried at 80 ° C. for 10 minutes, heat-cured at 190 ° C. for 40 minutes, and then left at 210 ° C. for 10 minutes to compare spectral waveforms. The heat resistance was compared.
First, using the same spectrophotometer as in Example 1, the optical filters of Examples 1 to 3 and Comparative Example 1 were 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. Later spectral waveforms were measured. For comparison of short-term heat resistance, the absorbance at the maximum absorption wavelength of the optical filters of Examples 1 to 12 and Comparative Examples 1 to 3 was used, and after thermosetting (190 ° C., The residual ratio of the absorbance after 40 minutes) and the residual ratio of the absorbance after the short-term heat test (210 ° C., 10 minutes) relative to the absorbance after thermosetting (190 ° C., 40 minutes) were calculated and compared. By this comparison, an optical filter having a higher residual rate of near-infrared absorbing dye means that it has excellent short-term heat resistance. The calculation method is the following formula (I) and formula (II). The calculation results are shown in Table 2 together with the results of long-term heat resistance comparison described later.

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

[Long-term heat resistance comparison]
In the optical filters obtained in Examples 1 to 3 and Comparative Example 1, the change in spectral waveform when the optical filter obtained by thermosetting at 190 ° C. for 40 minutes was left at a temperature of 125 ° C. was compared. The long-term heat resistance was compared.
First, using the same spectrophotometer as in Example 1, each of the optical filters in Examples 1 to 3 and Comparative Example 1 was dried at 80 ° C. for 10 minutes, and then the spectral waveform after thermosetting at 190 ° C. for 40 minutes was measured. This was taken as the initial waveform of the spectral waveform. For comparison of long-term heat resistance, the absorbance at the maximum absorption wavelength of the optical filters of Examples 1 to 3 and Comparative Example 1 was used. The time which became 0.8 times with respect to the light absorbency after minute hardening was made into the long-term heat-resistant lifetime, and each was compared. By this comparison, it means that the longer the long-term heat-resistant life, the better the long-term heat resistance. The results are shown in Table 2 together with the results of the short-term heat resistance comparison described above.

  As is clear from the results in Table 2, in comparison with Comparative Example 1, Examples 1 to 3 were high in both short-term heat resistance and long-term heat resistance. From the above, in the present invention, a thermosetting resin composition containing a thermosetting resin composed of a near infrared absorbing dye (A), an organic salt (B), and an epoxy resin (C) is a near infrared cut filter. The results showed excellent long-term heat resistance for manufacturing.

The thermosetting resin composition of the present invention and the near-infrared cut filter (optical filter) obtained thereby have a low deterioration in near-infrared absorption performance and high weather resistance even when a thermal load is applied. Since a near-infrared cut filter can be produced by simply forming a film by this method and the processability is also high, an optical filter for various applications, particularly a near-infrared cut filter for an image sensor such as a CCD or CMOS (optical filter) ) Is very useful.

Claims (12)

Near-infrared absorbing dye (A), an organic salt (B) composed of an anion other than tris (trifluoromethanesulfonyl) methide anion and a cation of a metal ion or an onium ion, and an epoxy resin (C) Resin composition. 2. The thermosetting resin composition according to claim 1, wherein the near-infrared absorbing dye (A) contains at least one of a cyanine compound and a diimonium compound. The near-infrared absorbing dye (A) contains at least one of a cyanine compound represented by the following formula (1) or formula (2) and a diimonium compound represented by the following formula (5). The thermosetting resin composition according to claim 1 or 2.

(In the formula (1) and the formula (2), R ₁ each independently of carbon atoms 1 to 5 an optionally substituted alkyl group or an alkoxy having 1 to 5 carbon atoms which may have a substituent R ₂ represents a halogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms or a nitro group, p is Represents an integer of 0 or 1, D is either the following formula (3) or formula (4), and X ⁻ represents a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion.

(In Formula (3), Y is any one of a hydrogen atom, a chlorine atom, an optionally substituted phenyl group, and an optionally substituted alkylamino group having 1 to 6 carbon atoms, * Indicates a binding site.)

(In Formula (4), Y is any one of a hydrogen atom, a chlorine atom, an optionally substituted phenyl group, and an optionally substituted alkylamino group having 1 to 6 carbon atoms, * Indicates a binding site.)

(In Formula (5), each R ₃ independently represents a C 1-7 alkyl group which may have a substituent or a C 1-5 alkoxyalkyl group which may have a substituent, X ⁻ is a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion. The organic salt (B) is a metal ion selected from lithium ion, sodium ion, potassium ion, rubidium ion or cesium ion, or an onium ion selected from nitrogen onium ion, phosphorus onium ion or sulfur onium ion, and methylbenzene sulfonate ( CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ ), carboxybenzene sulfonate (COOH (C ₆ H ₄ ) SO ₃ ⁻ ), benzoate (C ₆ H ₅ COO ⁻ ), trifluoroacetate (CF ₃ COO ⁻ ), trifluoro b methanesulfonate _(CF 3 SO ₂ ^-), tetra benzyl borate _{(B (C 6 H 5)} 4 -), bis (trifluoromethanesulfonyl) of claims 1 to 3, characterized in that it consists of anion selected from anion Any one Thermosetting resin composition. The organic salt (B) comprises a metal ion selected from lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion, and a bis (trifluoromethanesulfonyl) imide anion. The thermosetting resin composition according to claim 1. The thermosetting resin composition according to any one of claims 1 to 5, wherein an epoxy equivalent of the epoxy resin (C) is 150 to 600 g / eq. A polymer in which the epoxy resin (C) is composed only of a glycidyl methacrylate skeleton, or a combination of a glycidyl methacrylate skeleton mainly of acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, or a vinyl-substituted aromatic compound. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a copolymer. The thermosetting resin composition according to any one of claims 1 to 7, wherein the epoxy resin (C) is an epoxy compound having a fluorene skeleton. The near-infrared absorbing dye (A) contains at least one of cyanine compounds represented by the following formula (6) or formula (7). The thermosetting resin composition as described.

(In the formulas (6) and (7), R ₄ each independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxy group, An ethyl group, an n-butoxyethyl group, Y is a hydrogen atom or a chlorine atom, and X ⁻ is a tris (trifluoromethanesulfonyl) methide anion or a bis (trifluoromethanesulfonyl) imide anion.) A cured product of the thermosetting resin composition according to any one of claims 1 to 9. The near-infrared cut filter shape | molded using the thermosetting resin composition as described in any one of Claims 1 thru | or 10. An image sensor comprising the near infrared cut filter according to claim 11.