JP2017137401A - Thermosetting resin composition comprising phosphonium salt as resin curing accelerator, and near-infrared cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition comprising a near-infrared absorbing dye that can be thermally cured at low temperature and in a short time, and a near-infrared cut filter obtained by using the same.SOLUTION: The problem is solved by a thermosetting resin composition comprising quaternary phosphonium salt as a resin curing accelerator.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition containing a quaternary phosphonium salt as a resin curing accelerator, and a near-infrared cut filter (optical filter) having high heat resistance 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 around 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 near-infrared light in front of the image sensor to correct the human eye's visual sensitivity. It is known that

  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 having near infrared absorption ability is very expensive. Moreover, since it is glass, there exists a problem in workability, the freedom degree of design of an optical characteristic is narrow, and the response | compatibility to a spherical surface is also complicated. Further, there is a limit to reducing the thickness of the glass, and there are problems in securing space and reducing the weight when incorporating it into the imaging optical system. Therefore, it has been desired to develop a resin incorporating a near-infrared absorbing ability for manufacturing 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 is performed by coating the image pick-up element surface or the filter base-material surface with the coating liquid containing a near-infrared absorption pigment | dye. In Patent Document 2, a near-infrared cut filter using a cyanine compound as a near-infrared absorbing dye and an epoxy resin as a thermosetting resin is produced. However, when a high load is applied to thermosetting at 150 ° C. for 3 hours, the cyanine compound and the epoxy resin are thermally deteriorated, which leaves a problem in the manufacturing process of the near-infrared cut filter.

  Therefore, in order to solve the above-mentioned problems related to heat resistance, development of a thermosetting resin composition that can be thermoset at a lower temperature in a shorter time and a near-infrared cut filter using these are strongly desired.

JP-A 62-128943 JP2015-034252

  An object of this invention is to provide the thermosetting resin composition containing the near-infrared absorptive pigment | dye thermosetting at low temperature for a short time, and the near-infrared cut filter using these.

  In order to solve the above problems, the present inventors have intensively studied, and as a result, a thermosetting resin composition comprising a resin curing accelerator comprising a quaternary phosphonium salt, a cyanine compound, and an epoxy resin having a fluorene skeleton, and the same. It has been found that the near-infrared cut filter used solves the above-mentioned problems, 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表し、Ｒ_２はハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基又はニトロ基、ｑは０又は１の整数を表し、Ｄは下記式（３）又は式（４）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、フェニル基のいずれかであり、＊は結合部位を表し、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。）

（Ｂ）分子内にフルオレン骨格を有するエポキシ樹脂、
（Ｃ）分子内にカルボキシル基を２つ以上、もしくはカルボン酸無水物基を一つ以上有するエポキシ樹脂硬化剤、
（Ｄ）分子内に第４級ホスホニウム塩を有する樹脂硬化促進剤、
［２］近赤外線吸収色素（Ａ）が下記式（５）又は式（６）のいずれかで表されるシアニン化合物であることを特徴とする［１］に記載の熱硬化性樹脂組成物、

（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表し、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、フェニル基のいずれかであり、Ｘ⁻はトリス（トリフルオロメタンスルホニル）メチドアニオンである。）
［３］式（３）乃至式（６）におけるＹが水素原子、メチル基、アセトキシ基、又はフェニル基である［１］又は［２］に記載の熱硬化性樹脂組成物、
［４］式（１）、式（２）、式（５）および式（６）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［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］式（７）で表される分子内にフルオレン骨格を有するエポキシ樹脂を含むことを特徴とする［１］乃至［４］のいずれか一つに記載の熱硬化性樹脂組成物、

（式中、環Ｚはそれぞれ独立にベンゼン環を含む縮合多環式芳香族炭化水素環、Ｒ_３およびＲ_４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_５はそれぞれ独立に水素原子又はメチル基を表し、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。）
［６］式（７）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［５］に記載の熱硬化性樹脂組成物、
［７］［１］乃至［６］のいずれか一つに記載の熱硬化性樹脂組成物の硬化物、
［８］［１］乃至［７］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、
［９］［８］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 thermosetting resin composition comprising the following (A) to (D):
(A) a cyanine compound represented by the following formula (1) or formula (2) as a near-infrared absorbing dye,

(In the formula, each R ₁ independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms, and R ₂ represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 is an alkoxy group or a nitro group, q is an integer of 0 or 1, D is any of the following formula (3) or formula (4), Y is a hydrogen atom, a chlorine atom, an acyloxy group, or a carbon number of 1 5 alkyl group is either a phenyl group, * represents a binding site, X ^- is a tris (trifluoromethanesulfonyl) methide anion).

(B) an epoxy resin having a fluorene skeleton in the molecule;
(C) an epoxy resin curing agent having two or more carboxyl groups or one or more carboxylic anhydride groups in the molecule;
(D) a resin curing accelerator having a quaternary phosphonium salt in the molecule;
[2] The thermosetting resin composition according to [1], wherein the near-infrared absorbing dye (A) is a cyanine compound represented by either the following formula (5) or formula (6):

(In the formula, each R ₁ independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms, and Y represents a hydrogen atom, a chlorine atom, an acyloxy group, or an alkyl group having 1 to 5 carbon atoms. And any one of the phenyl groups, and X ⁻ is a tris (trifluoromethanesulfonyl) methide anion.)
[3] The thermosetting resin composition according to [1] or [2], wherein Y in the formulas (3) to (6) is a hydrogen atom, a methyl group, an acetoxy group, or a phenyl group,
[4] R ₁ in formula (1), formula (2), formula (5) and formula (6) is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl The thermosetting resin composition according to any one of [1] to [3], which is a group, a sec-butyl group, a t-butyl group, or a methoxyethyl group,
[5] The thermosetting resin composition according to any one of [1] to [4], including an epoxy resin having a fluorene skeleton in a molecule represented by the formula (7),

(Wherein ring Z are each fused independently containing a benzene ring polycyclic aromatic hydrocarbon ring, R ₃ and R ₄ are each independently a cyano group, a halogen atom, an alkyl group, selected from aryl groups, R ₅ 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.)
[6] The thermosetting resin composition according to [5], wherein two rings Z in formula (7) are both benzene rings,
[7] A cured product of the thermosetting resin composition according to any one of [1] to [6],
[8] A near-infrared cut filter formed using the thermosetting resin composition according to any one of [1] to [7],
[9] An image sensor provided with the near infrared cut filter according to [8],
About.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can produce a near-infrared cut filter with a low-temperature and short-time thermosetting process was able to be provided.

  The thermosetting resin composition of the present invention containing the near-infrared absorbing dye (A), the epoxy resin (B), the epoxy resin curing agent (C), and the resin curing accelerator (D) will be described in detail.

The near-infrared absorbing dye (A) used in the present invention is represented by the above formula (1) or formula (2), and R _{1 in} both formulas is independently an alkyl group having 1 to 5 carbon atoms or 1 to 1 carbon atoms. 5 represents an alkoxyalkyl group, any of which may have a substituent.

In R ₁ of formula (1) or 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 an 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 and the like.

In R ₁ of formula (1) or 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, a propoxyethyl group. N-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, methoxyethoxymethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group, etc. It is done.

In R ₁ of formula (1) or formula (2), the substituent that the alkyl group having 1 to 5 carbon atoms may have is not particularly limited, and 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, 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 in} formula (1) or formula (2) 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, and an ethyl group, An n-butyl group and a methoxyethyl group are particularly preferable.

In R ₁ of formula (1) or formula (2), the substituent that the alkoxyalkyl group having 1 to 5 carbon atoms may have 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.

In Formula (1) or Formula (2), R ₂ represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a nitro group, q represents an integer of 0 or 1, Any of the alkyl group having 1 to 5 and the alkoxy group having 1 to 5 carbon atoms may have a substituent.

In R ₂ of formula (1) or formula (2), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom, a chlorine atom, and an iodine atom are preferable, and a chlorine atom is particularly preferable. .

In R ₂ of formula (1) or formula (2), an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms have the same meaning as R ₁ in formula (1) or formula (2).

X in formula (1) or (2) ^- is a tris (trifluoromethanesulfonyl) methide anion.

  The bonding group D in the formula (1) or the formula (2) is represented by the above formula (3) or the formula (4), and * represents a binding site. Y in Formula (3) and Formula (4) 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 a chlorine atom, a methyl group, or a phenyl group is preferable.

  In Y of Formula (3) and Formula (4), the acyloxy group means a group obtained by removing a hydrogen atom from a carboxyl group (—COOH) of a carboxylic acid, and is not particularly limited. Examples include a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, and a trifluoroacetyloxy group, and an acetoxy group is preferable.

  In Y of Formula (3) and Formula (4), 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, 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. preferable.

  The phenyl group of Y in the above formulas (3) and (4) 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 cyanine compound having a cation moiety represented by the above formula (1) or formula (2), and the above formula having the above formula (3) and formula (4) as a linking group D. A cyanine compound having a cation moiety represented by (5) or formula (6) is particularly preferred. In formula (5) or formula (6), R ₁ and X ⁻ have the same meaning as in formula (1) or formula (2).

The cyanine compound used in the present invention can be synthesized, for example, by the following method with reference to the method described in JP-A-2008-88426.

  1 mol of the compound represented by the above formula (8) and 1 mol of methyl isopropyl ketone are usually present in an organic solvent such as ethanol in the presence of an acid catalyst, for example, at 20 ° C. to 130 ° C., usually for 30 minutes to 5 hours. The indolenine compound represented by the above formula (9) can be synthesized by heating.

R ₂ and q in the above formula (8) and formula (9) have the same meaning as in formula (1) or formula (2).

  Although it does not restrict | limit especially with the acid catalyst for synthesize | combining the indolenine compound represented by the said Formula (9), For example, hydrochloric acid, an acetic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium, etc. Is mentioned.

  1 mol of the compound represented by the above formula (9) and an aliphatic hydrocarbon compound having 1 to 5 carbon atoms which may have a substituent having a leaving group such as a halogeno group or a tosyl group, or a substituent 1 mole of an alkoxy-substituted aliphatic hydrocarbon compound having 1 to 5 carbon atoms, which may have a hydrogen atom, if necessary, in an organic solvent such as acetonitrile, for example, usually heated at 20 to 150 ° C. for 1 to 5 hours, A compound represented by the above formula (10) can be synthesized.

A ^{− in the} above formula (10) is an anion derived from the leaving group of the alkylating agent or alkoxyalkylating agent used in the above synthesis, and R ₁ in formula (1) or formula (2) It is synonymous with.

（式（１１）および式（１２）のＤは式（３）又は式（４）におけるのと同義である。） 2 moles of the compound represented by the formula (10), 1 mole of the compound represented by the following formula (11) or the formula (12), further tris (trifluoromethanesulfonyl) methido acid or its sodium salt, potassium salt, etc. 1 mol of salt is added in the presence of a base catalyst such as sodium acetate, potassium acetate, piperazine, piperidine, triethylamine or the like, in an organic solvent such as ethanol, acetic anhydride or acetic anhydride and glacial acetic acid, for example, 50 to The cyanine compound represented by Formula (1) or Formula (2) used in the present invention can be synthesized by performing a condensation reaction at 140 ° C. for usually 10 minutes to 10 hours, preferably 30 minutes to 4 hours.

(D in Formula (11) and Formula (12) has the same meaning as in Formula (3) or Formula (4).)

Specific examples of the cyanine compound represented by the formula (1) or the formula (2) used in the present invention include the following compounds 1 to 16, but are not limited thereto.

  The near-infrared cut filter of the present invention may contain a near-infrared absorbing dye other than the formula (1) or the formula (2) as necessary for the purpose of preparing the near-infrared region.

  Examples of near infrared absorbing dyes that can be used in combination include cyanine, phthalocyanine, naphthalocyanine, diimonium, squarylium, croconium, diketopyrrolopyrrole, polymethine, metal dithiol complex, porphyrin, azomethine, Examples include, but are not limited to, oxonol-based compounds, and any organic compound having near-infrared absorption ability may be used.

  Examples of near-infrared absorbing pigments of inorganic metals that can be used in combination include copper compounds such as metallic copper or copper sulfide, copper oxide, copper phosphate complexes, copper sulfonate complexes, mixtures containing zinc oxide as a main component, tungsten compounds, oxidation Examples thereof include, but are not limited to, a mixture containing titanium as a main component, and any inorganic compound that absorbs near infrared rays may be used. When these do not dissolve in the resin composition of the present invention, they can be mixed and dispersed by the following method.

  When the near-infrared absorbing dye contained in the near-infrared cut filter of the present invention does not dissolve in the resin composition of the present invention, it can be used by mixing with other components while dispersing the insoluble dye in fine particles. .

  Examples of the dispersion method include a known method using 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. In the pulverization of the pigment particles in the sand mill (bead mill), it is preferable to use beads having a small particle diameter, and to perform the treatment under conditions that increase 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.

  The epoxy resin (B) used in the present invention is represented by the above formula (7) having a fluorene skeleton (hereinafter abbreviated as fluorene).

  In the above formula (7), the condensed polycyclic aromatic hydrocarbon ring represented by ring Z is a condensed bicyclic hydrocarbon ring (for example, a C8-C20 condensed bicyclic ring such as an indene ring or a naphthalene ring). A condensed bicyclic hydrocarbon ring such as a hydrocarbon ring, preferably a C10-C16 condensed bicyclic hydrocarbon ring), a condensed tricyclic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.), and the like. It is done. 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 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 or 2 -A naphthyl group etc. may be sufficient and 2-naphthyl group is especially preferable.

R _{3 in the} above formula (7) is, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl group (C6-C10 aryl such as phenyl group) Non-reactive substituents, such as a group) etc., and especially a halogen atom, a cyano group, or an alkyl group in many cases. Examples of the alkyl group include C1-C6 alkyl groups 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 such as a methyl group). In addition, when x is plural (2 or more), R ₃ may be the same or different from each other. Moreover, R < ₃ > substituted by the two benzene rings which comprise fluorene may be the same or different. Further, the bonding position (substitution position) of R ₃ with respect to the benzene ring constituting the fluorene is not particularly limited. The substitution number x is preferably 0 to 1, and particularly preferably 0. In the two benzene rings constituting fluorene, the number of substitutions x may be the same or different from each other.

Examples of the substituent R ₄ of the ring Z include an alkyl group (for example, a C1-C12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C1-C8 alkyl group, more preferably C1-C6 alkyl group etc.), cycloalkyl group (C5-C8 cycloalkyl group such as cyclohexyl group, preferably C5-C6 cycloalkyl group etc.), aryl group (for example, phenyl group, tolyl group, xylyl group, etc.) C6-C14 aryl group, preferably C6-C10 aryl group, more preferably C6-C8 aryl group, etc.), aralkyl group (C6-C10 aryl-C1-C4 alkyl group such as benzyl group, phenethyl group, etc.), etc. Hydrocarbon group; alkoxy group (C1-C8 alkoxy group such as methoxy group, preferably C1-C6 alkoxy group, etc. ), A cycloalkoxy group (C5-C10 cycloalkyloxy group, etc.), an aryloxy group (C6-C10 aryloxy group, etc.) and the like -OR ₆ [wherein R ₆ is a hydrocarbon group (the same hydrocarbon as described above) Group). An alkylthio group (a C1-C8 alkylthio group such as a methylthio group, preferably a C1-C6 alkylthio group, etc.) or the like —SR ₆ (wherein R ₆ is the same as above); an acyl group (such as an acetyl group) C1-C6 acyl group, etc.); alkoxycarbonyl group (C1-C4 alkoxy-carbonyl group, such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom); hydroxyl group; nitro group; Group; substituted amino group (for example, dialkylamino group such as dimethylamino group) and the like.

Of these, R ₄ 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. [For example, an alkyl group (for example, C1-C6 alkyl group)], an alkoxy group (C1-C4 alkoxy group etc.), and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) are particularly preferable.

The substituents R ₄ of the two rings Z may be the same or different. In the same ring Z, when the number of substituents y of the substituent R ₄ is 2 or more, they may be the same or different from each other. The number 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 _{5 in the} above formula (7) 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 (7) (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. The substitution position on the ring Z of the glycidyloxy group is not particularly limited as long as it is substituted at an appropriate position.

  The number n of ethyleneoxy chains in the glycidyloxy group of the formula (7) 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 preferable.

  Examples of the compound represented by the formula (7) 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 [for example, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5-glycidyloxy- 1-naphthyl) fluorene and the like], and the like. In the above formula (7), the number of substituents z is 1, and n is 0.

  As an epoxy equivalent of the epoxy compound which has a fluorene, 150-1000 g / eq. Is preferable, 150-800 g / eq. Is more preferable, 150-400 g / eq. Is further more preferable, 150-350 g / eq. Is especially preferable. These are easily available from the market, and examples include Ogsol PG-100 and Ogsol CG-500 manufactured by Osaka Gas Chemical Co., Ltd.

  The epoxy resin represented by Formula (7) used by this invention may be used 1 type or in mixture of 2 or more types.

  In addition, although the thermosetting resin composition of this invention contains the epoxy resin represented by the said Formula (7), if it is a range which does not inhibit the effect of this invention, it may contain the other epoxy resin. . 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 fluorene and the like. 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 (7) to the whole epoxy resin component is usually 50 to 99.5% by mass, preferably 70 to 97% by mass, 90 -98 mass% is more preferable.

  The epoxy resin curing agent (C) used in the present invention is not particularly limited as long as it has two or more carboxyl groups or one or more carboxylic anhydride groups in the molecule. Can be used.

  The number of carbon atoms constituting the epoxy resin curing agent is usually 2 to 200, preferably 2 to 80 carbon atoms, more preferably 3 to 60 carbon atoms, and particularly preferably 4 to 40 carbon atoms.

  Examples of carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Methyl hexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3 -Carboxylic anhydrides such as dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride An acid anhydride having 4 to 40 carbon atoms in the skeleton that constitutes the skeleton is exemplified. 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. In addition, when a geometric isomer or an optical isomer exists, it is not particularly limited. 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; multimers of unsaturated fatty acids such as linolenic acid and oleic acid and dimer acid compounds that are reduced products thereof; 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] hept -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, A polyvalent carboxylic acid compound having a bicyclo structure such as 5-dicarboxylic acid can be used.

  In addition, a polyvalent carboxylic acid obtained by reacting a commercially available bifunctional or higher functional alcohol compound with a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid can be used, for example, an anhydride or a polyvalent carboxylic acid. Examples of the alcohol compound include, but are not limited to, geometric isomers or optical isomers, and include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentane. Diol, 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-butane All, 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-1H-4,7-methanoindenyldimethanol Examples thereof include organic aliphatic alcohols having 2 to 30 carbon atoms.

  The resin curing accelerator (D) is not particularly limited as long as it has one or more quaternary phosphonium salts in the molecule, and those known per se can also be used.

  The number of phosphorus atoms constituting the resin curing accelerator is usually 1 to 10, preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 3.

  Examples of the quaternary phosphonium salt include ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, n-butyltriphenylphosphonium dicyanamide, tetraphenylphosphonium bromide, n-butyltrimide. Phenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium decanoate, acetonyltriphenylphosphonium chloride, amyltriphenylphosphonium bromide, trans-2-butene-2,4-bis (triphenylphosphonium chloride), (2- Chlorobenzyl) triphenylphosphonium chloride, (4-chlorobenzyl) triphenylphosphonium chloride Loride, 2-dimethylaminoethyltriphenylphosphonium bromide, (methoxymethyl) triphenylphosphonium chloride, tributylhexadecylphosphonium bromide, Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.), Hishicolin PX-4MC (Nippon Chemical Industry Co., Ltd.) Product), Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.), U-CAT5003 (San Apro Co., Ltd.) and the like. Tetrabutylphosphonium bromide, n-butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tributylhexadecylphosphonium bromide, Hishicolin PX-4MP, Hishicolin PX-4MC, Hishicolin PX-4ET, U-CAT5003, etc. are transparent and cured. Particularly preferable from the viewpoint of temperature. The resin curing accelerators may be used alone or in combination of two or more.

  The addition rate of the quaternary phosphonium salt is preferably 0.001 to 30 parts by mass and 0.05 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin represented by the above formula (7). More preferably, it is 10 mass parts.

  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. Although a coupling agent is used as needed, it is 0.05-20 mass% normally with respect to 1 mass part of thermosetting resin compositions of this invention, Preferably 0.1-10 mass% 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. Thus, the average particle size of the nano-order level inorganic filler used for ensuring transparency is preferably 500 nm or less, and particularly preferably 200 nm or less. 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. As the content of these inorganic fillers, an amount occupying 0 to 95% by mass in the thermosetting resin composition of the present invention is used.

  The near-infrared cut filter of the present invention can contain an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant to prevent coloring.

  Examples of the light stabilizer 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 -Mixed esterified product of piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (2-decanoic acid) (2 , 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6,- Tramethyl-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] me L) 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]] , 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 Lu-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-tetrahydrophthalimide) -Methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di- tert-pentylphenyl) benzotriazole, reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol, 2- (2H- Benzotriazole such as benzotriazol-2-yl) -6-dodecyl-4-methylphenol Compound, benzoate series such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-[(hexyl) oxy] phenol and other triazine compounds, and the like. Among them, hindered amine compounds are particularly preferable.

  A commercially available product can be used as the amine compound of the light stabilizer, but the commercially available amine compound is not particularly limited. For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, and TINUVIN622LD are manufactured by Ciba Specialty Chemicals. TINUVIN152, CHIMASSORB 944; manufactured by ADEKA, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.

  The phosphorus compound of the antioxidant is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearylpentaerythritol diphos Phyto, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phosphite, dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert- Butylphenyl 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 ′ -Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphospho Knight, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-) -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, Examples include trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is.

  Commercially available products may be used as the phosphorus compound as the antioxidant, and they are not particularly limited. For example, as ADEKA, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36 Adeka tab HP-10, Adeka tab 2112, Adeka tab 260, Adeka tab 522A, Adeka tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP, and the like.

  One phenol 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-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) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythris Til-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-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.

  Commercially available products can be used as the above phenolic compounds, and they are not particularly limited. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1020, IRGANOX 1020, LGANOX 1020 ADK STAB AO-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; As a product, Sumilizer GA-80, Sumilizer MDP S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

  As an additive that can be used in combination as necessary, it is preferable to contain at least one of an amine compound as a light stabilizer, a phosphorus compound as an antioxidant, and a phenol compound, and the addition rate is particularly limited. However, it is preferably used in the range of 0.005 to 5.0% by mass with respect to 1 part by mass of the thermosetting resin composition of the present invention.

  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 (thermal stabilizer, antioxidant, ultraviolet ray). Absorbents, etc.), fillers, antistatic agents, flame retardants, flame retardant aids and the like. Diluents and additives may be used alone or in combination of two or more.

  The near-infrared cut filter (optical filter) obtained by 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-made 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.

  The content of the near-infrared absorbing pigment used in the thermosetting resin composition of the present invention is appropriately determined according to the target near-infrared cut rate. Examples of the resin base material used include polyethylene, polycycloalkane, polycycloolefin, polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl fluorides. Compounds, and addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, poly (vinylidene cyanide), vinylidene fluoride / trifluoroethylene copolymers, vinylidene fluoride / tetrafluoro Contains fluorine compounds such as ethylene copolymers, vinyl compounds such as vinylidene cyanide / vinyl acetate copolymers or copolymers of fluorine compounds, polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Resin, polyamide such as nylon 6 and nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polyether such as polycarbonate and polyoxymethylene, epoxy resin, 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, the following known methods can be used. 1) A near-infrared absorbing dye and a resin curing accelerator are dissolved in a thermosetting resin and a curing agent to produce the thermosetting resin composition of the present invention, and after molding, heat curing is performed to produce a resin plate or film. Method 2) A method of producing a thermosetting resin composition of the present invention containing a near-infrared absorbing dye and a resin (adhesive), and producing a laminated resin plate, a laminated resin film, or a laminated glass plate. .

  In the method 1), a near-infrared absorbing dye and a resin curing accelerator are dissolved in a thermosetting resin and a curing agent, and injected into a mold and cured by heating or poured into a mold. And a method of forming by heat reaction until a hard product is obtained. The processing temperature, filming (resin plate) conditions, etc. are somewhat different depending on the composition used, but curing conditions of about 30 minutes to 3 hours at 100 to 140 ° C. are usually applied. The amount of the near-infrared absorbing dye added varies depending on the thickness, absorption strength, visible light transmittance, etc. of the resin plate or film to be produced, but is usually about 0.01 to 30% by mass with respect to 1 part by mass of the base resin. Preferably, about 0.01 to 15% by mass is used.

  In the method 2), a near-infrared absorbing dye is added to a known transparent adhesive for laminated glass such as silicon-based, urethane-based, acrylic-based resin, polyvinyl butyral adhesive, ethylene-vinyl acetate adhesive, etc. . Using an added resin of about 1 to 30% by mass, an optical filter is produced by bonding transparent resin plates, resin plates and resin films, resin plates and glass, resin films, resin films and glass, and glasses. To do. When kneading and mixing by each method, additives usually used for resin molding such as an ultraviolet absorber and a plasticizer may be added.

  The near-infrared cut filter (optical filter) of the present invention is used not only for image sensor applications and display front plates, but also for filter films that need to cut near-infrared rays, such as heat insulating films, optical products, and sunglasses. I can do it.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” means “parts by mass” unless otherwise specified. The present invention is not limited to these examples.

[Synthesis Example 1]
(Synthesis of 5-fluoro-2,3,3-trimethyl-3H-indole)
To a 200 ml four-necked flask, add 40 ml of ethanol, 6.7 g of isopropyl methyl ketone, 8.4 g of 4-fluorophenylhydrazine hydrochloride and 19 g of p-toluenesulfonic acid monohydrate, and stir at reflux temperature for 7 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, the organic layer is recovered, and the organic solvent is distilled off under reduced pressure to remove 5-fluoro-2,3,3-trimethyl- 8 g of 3H-indole was obtained.

[Synthesis Example 2]
(Synthesis of 1-methoxyethyl-5-fluoro-2,3,3-trimethyl-3H-indolenin)
To a 100 ml three-necked flask, 8 g of 5-fluoro-2,3,3-trimethyl-3H-indole, 16 g of methoxyethyl p-toluenesulfonate, 9.6 g of potassium carbonate, and 15 ml of water were added and refluxed. Stir for 7 hours. After completion of the heating, the reaction solution was cooled to room temperature, ethyl acetate was added, and the mixture was separated, and the solvent of the organic layer was distilled off under reduced pressure to give 1-ethyl-5-fluoro-2,3,3-trimethyl-3H-. 8 g of indolenine was obtained.

[Synthesis Example 3]
(Synthesis of 7-fluoro-2,3,3-trimethyl-3H-indole)
30 ml of ethanol, 3.7 g of isopropyl methyl ketone, 5 g of 2-fluorophenylhydrazine hydrochloride and 11 g of p-toluenesulfonic acid monohydrate were added to a 100 ml three-necked flask, and the mixture was stirred at reflux temperature for 2 hours. 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 obtain 7-fluoro-2,3,3-trimethyl-3H-indole. 5 g was obtained.

[Synthesis Example 4]
(Synthesis of 1-methoxyethyl-7-fluoro-2,3,3-trimethyl-3H-indolenin)
To a 100 ml three-necked flask, add 8 g of 7-fluoro-2,3,3-trimethyl-3H-indole, 16 g of methoxyethyl p-toluenesulfonate, 9.6 g of potassium carbonate, and 15 ml of water at reflux temperature. Stir for 7 hours. After completion of the heating, the reaction solution is cooled to room temperature, ethyl acetate is added, and the mixture is separated, the organic layer is recovered, and the organic solvent is distilled off under reduced pressure to give 1-ethyl-7-fluoro-2,3,3-trimethyl. 7.6 g of -3H-indolenin was obtained.

[Synthesis Example 5]
(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 gradually 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.

[Synthesis Example 6]
(Synthesis of Compound 7)
In a 100 ml four-necked flask, 3.3 g of 1-methoxyethyl-5-fluoro-2,3,3-trimethyl-3H-indolenin, N-phenyl-2-phenyl-3-[(phenylamino) methylene] 1 g of -1-cyclohexene-1-methanimine hydrochloride, 2.8 g of potassium salt of tristrifluoromethanesulfonylmethide, 1.2 g of sodium acetate, 10 ml of acetic acid and 10 ml of acetic anhydride were added and refluxed for 4 hours. Stir. The reaction solution was cooled to room temperature, 200 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) and recrystallized from ethyl acetate and hexane to obtain 0.13 g of Compound 7.
Mass spectrum M + = 649
Maximum absorption wavelength 759nm (methanol)

[Synthesis Example 7]
(Synthesis of Compound 8)
In a 100 ml four-necked flask, 2.5 g of 1-ethyl-7-fluoro-2,3,3-trimethyl-3H-indolenin, N-phenyl-2-phenyl-3-[(phenylamino) methylene]- 1.5 g of 1-cyclohexene-1-methanimine hydrochloride, 2.5 g of potassium tristrifluoromethanesulfonylmethide, 1.2 g of sodium acetate, 15 ml of acetic acid and 15 ml of acetic anhydride were added, and the mixture was refluxed for 4 hours. Stir. The reaction solution was cooled to room temperature, 200 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 8.
Mass spectrum M + = 589
Maximum absorption wavelength 754nm (methanol)

[Synthesis Example 8]
(Synthesis of epoxy resin curing agent based on JP2014-80857)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 204 g of methyl ethyl ketone (hereinafter MEK), 294 g of tricyclodecane dimethanol, 4-methylcyclohexane-1,2-dicarboxylic anhydride ( 423 g of Shin Nippon Rika Co., Ltd., Ricacid MH) and 99 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical) were added and reacted at 50 ° C. for 2 hours. Thereafter, the reaction was further carried out at 70 ° C. for 4 hours. By adding 145 g of MEK to the obtained reaction solution, 1166 g of MEK solution of colorless epoxy resin curing agent having a concentration of 70% by mass was obtained.

[Example 1]
(Production of thermosetting resin composition containing compound 1 and quaternary phosphonium salt, 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 an epoxy resin (B), cyclohexanone 67 parts were added and dissolved by stirring at 20 to 35 ° C. for 2 hours. Next, as the near-infrared absorbing dye (A), the epoxy resin curing agent obtained in Synthesis Example 8 with 1.0 part of the above-mentioned compound 1 (see JP-A-2008-88426, λmax in methanol: 781 nm) ( 48 parts of C) and 0.5 part of a quaternary phosphonium salt (manufactured by Nippon Chemical Industry Co., Ltd., Hishicolin PX-4MP) as a resin curing accelerator (D) are added until uniform at 20 to 35 ° C. The thermosetting resin composition of this invention was obtained by stirring. 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 130 ° C. for 30 minutes to obtain a near infrared cut filter.
The obtained near-infrared cut filter was measured using a spectrophotometer (Shimadzu Corporation, UV-visible spectrophotometer UV-3150), and the absorbance of the near-infrared cut filter was measured in the range of 300 to 1100 nm at a sampling pitch of 1 nm. . The near-infrared cut filter after spectroscopic measurement was immersed in cyclohexanone for 2 minutes, then dried at 100 ° C. for 2 minutes to remove the solvent, and the solvent resistance was tested by measuring the absorbance of the near-infrared cut filter in the same manner. The filter having a small decrease in absorbance was excellent in solvent resistance, and it was judged that the thermosetting reaction had proceeded at 130 ° C. for 30 minutes. Table 1 shows the absorbance at the maximum absorption wavelength of the spectral waveform of the near-infrared cut filter.

[Example 2]
(Production of Compound 7, Thermosetting Resin Composition Containing Quaternary Phosphonium Salt, 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 1 except that Compound 7 obtained in Synthesis Example 6 was used instead of Compound 1. The results are shown in Table 1.

[Example 3]
(Production of thermosetting resin composition containing compound 8 and quaternary phosphonium salt, 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 1 except that Compound 8 obtained in Synthesis Example 7 was used instead of Compound 1. The results are shown in Table 1.

[Example 4]
(Production of thermosetting resin composition containing compound 10 and quaternary phosphonium salt, 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 1 except that Compound 10 (the compound of Example 4 of JP-A-2008-88426) was used instead of Compound 1. The results are shown in Table 1.

[Example 5]
(Production of thermosetting resin composition containing compound 13 and quaternary phosphonium salt, 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 1 except that Compound 13 (the compound of Example 3 of JP-A-2008-88426) was used instead of Compound 1. The results are shown in Table 1.

[Example 6]
(Production of thermosetting resin composition containing compound 1 and quaternary phosphonium salt, 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 1 except that U-CAT 5003 (manufactured by San Apro Co., Ltd.) was used instead of Hishicolin PX-4MP. The results are shown in Table 1.

[Example 7]
(Production of thermosetting resin composition containing compound 7 and quaternary phosphonium salt, 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 2 except that U-CAT 5003 (manufactured by San Apro Co., Ltd.) was used instead of Hishicolin PX-4MP. The results are shown in Table 1.

[Example 8]
(Production of thermosetting resin composition containing compound 8 and quaternary phosphonium salt, 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 U-CAT 5003 (manufactured by San Apro Co., Ltd.) was used instead of Hishicolin PX-4MP. The results are shown in Table 1.

[Example 9]
(Production of thermosetting resin composition containing compound 10 and quaternary phosphonium salt, 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 4 except that U-CAT 5003 (manufactured by San Apro Co., Ltd.) was used instead of Hishicolin PX-4MP. The results are shown in Table 1.

[Example 10]
(Production of thermosetting resin composition containing compound 13 and quaternary phosphonium salt, 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 U-CAT 5003 (manufactured by San Apro Co., Ltd.) was used instead of Hishicolin PX-4MP. The results are shown in Table 1.

[Comparative Example 1]
(Preparation of thermosetting resin composition containing compound 1 and near-infrared cut filter)
Production of a near-infrared cut filter in the same manner as in Example 1 except that 18% of Nikka Octix zinc (manufactured by Nippon Chemical Industry Co., Ltd.) is used as the resin curing accelerator (D) instead of Hishicolin PX-4MP. Spectral waveforms were measured. The results are shown in Table 1.

[Comparative Example 2]
(Preparation of thermosetting resin composition containing compound 1 and near-infrared cut filter)
Production of a near-infrared cut filter in the same manner as in Example 2 except that 18% of Nikka Octix zinc (manufactured by Nippon Chemical Industry Co., Ltd.) is used as the resin curing accelerator (D) instead of Hishicolin PX-4MP. Spectral waveforms were measured. The results are shown in Table 1.

[Comparative Example 3]
(Preparation of thermosetting resin composition containing compound 1 and near-infrared cut filter)
Production of a near-infrared cut filter in the same manner as in Example 3 except that 18% of Nikka Octix zinc (manufactured by Nippon Chemical Industry Co., Ltd.) is used as the resin curing accelerator (D) instead of Hishicolin PX-4MP. Spectral waveforms were measured. The results are shown in Table 1.

[Comparative Example 4]
(Preparation of thermosetting resin composition containing compound 1 and near-infrared cut filter)
Production of a near-infrared cut filter in the same manner as in Example 4 except that 18% of Nikka Octix zinc (manufactured by Nippon Chemical Industry Co., Ltd.) is used as the resin curing accelerator (D) instead of Hishicolin PX-4MP. Spectral waveforms were measured. The results are shown in Table 1.

[Comparative Example 5]
(Preparation of thermosetting resin composition containing compound 1 and near-infrared cut filter)
Production of a near-infrared cut filter in the same manner as in Example 5 except that 18% of Nikka Octix zinc (manufactured by Nippon Chemical Industry Co., Ltd.) is used as the resin curing accelerator (D) instead of Hishicolin PX-4MP. Spectral waveforms were measured. The results are shown in Table 1 below.

[Solvent resistance evaluation test]
In the near-infrared cut filters obtained in Examples 1 to 10 and Comparative Examples 1 to 5, the spectral waveform after standing at 130 ° C. for 30 minutes, immersed in cyclohexanone for 2 minutes, and then dried at 100 ° C. for 2 minutes. By comparing these, the solvent resistance was compared. The comparison of the solvent resistance is based on the absorbance at the maximum absorption wavelength of the near infrared cut filters of Examples 1 to 10 and Comparative Examples 1 to 5, and the solvent resistance against the absorbance after the thermosetting test (130 ° C., 30 minutes). The residual ratio was calculated from the absorbance after the test (dipped in cyclohexanone for 2 minutes and dried at 100 ° C. for 2 minutes), and each was compared. By this comparison, it means that the higher the residual ratio, the better the thermosetting property and the elution of the dye is prevented. The calculation method is the following formula (I). The calculation results are shown in Table 2 below.

(Remaining rate after solvent resistance test (dipped in cyclohexanone for 2 minutes and dried at 100 ° C. for 2 minutes)) = (absorbance after solvent resistance test) / (absorbance after heating (130 ° C., 30 minutes)) I)

  From the results of Table 2, Examples 1 to 10 showed a high residual rate even after the solvent resistance test compared to Comparative Examples 1 to 5. From the above, it was found that the thermosetting resin composition of the present invention containing a quaternary phosphonium salt as a resin curing accelerator exhibits excellent thermosetting in the production of the near infrared cut filter of the present invention. .

  The thermosetting resin composition containing a quaternary phosphonium salt and the near-infrared cut filter (optical filter) obtained by the present invention are most suitable for a thermosetting process at a lower temperature and in a shorter time than conventional products. Because it is a resin solution, it can be easily formed by a method such as spin coating and has excellent workability. Therefore, optical filters for various applications, particularly near infrared rays for image sensors such as CCD and CMOS. It is very useful as a cut filter.

Claims (9)

A thermosetting resin composition comprising the following (A) to (D).
(A) A cyanine compound represented by the following formula (1) or formula (2) as a near-infrared absorbing dye.

(In the formula, each R ₁ independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms, and R ₂ represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 is an alkoxy group or a nitro group, q is an integer of 0 or 1, D is any of the following formula (3) or formula (4), Y is a hydrogen atom, a chlorine atom, an acyloxy group, or a carbon number of 1 5 alkyl group is either a phenyl group, * represents a binding site, X ^- is a tris (trifluoromethanesulfonyl) methide anion).

(B) An epoxy resin having a fluorene skeleton in the molecule.
(C) An epoxy resin curing agent having two or more carboxyl groups or one or more carboxylic anhydride groups in the molecule.
(D) A resin curing accelerator having a quaternary phosphonium salt in the molecule. 2. The thermosetting resin composition according to claim 1, wherein the near-infrared absorbing dye (A) is a cyanine compound represented by either the following formula (5) or formula (6).

(In the formula, each R ₁ independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxyalkyl group having 1 to 5 carbon atoms, and Y represents a hydrogen atom, a chlorine atom, an acyloxy group, or an alkyl group having 1 to 5 carbon atoms. And any one of the phenyl groups, and X ⁻ is a tris (trifluoromethanesulfonyl) methide anion.) The thermosetting resin composition according to claim 1 or 2, wherein Y in the formulas (3) to (6) is a hydrogen atom, a methyl group, an acetoxy group, or a phenyl group. R ₁ in formula (1), formula (2), formula (5) and formula (6) is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec The thermosetting resin composition according to any one of claims 1 to 3, which is a -butyl group, a t-butyl group, or a methoxyethyl group. The thermosetting resin composition according to any one of claims 1 to 4, comprising an epoxy resin having a fluorene skeleton in the molecule represented by the formula (7).

(Wherein ring Z are each fused independently containing a benzene ring polycyclic aromatic hydrocarbon ring, R ₃ and R ₄ are each independently a cyano group, a halogen atom, an alkyl group, selected from aryl groups, R ₅ 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 thermosetting resin composition according to claim 5, wherein in the formula (7), the two rings Z are both benzene rings. Hardened | cured material of the thermosetting resin composition as described in any one of Claims 1 thru | or 6. The near-infrared cut filter shape | molded using the thermosetting resin composition as described in any one of Claims 1 thru | or 7. An imaging device comprising the near-infrared cut filter according to claim 8.