JP6833763B2 - Ethylene compound, UV absorber and resin composition - Google Patents

Description

The present invention relates to an ethylene compound capable of absorbing light in the ultraviolet to purple region, a resin composition containing the ethylene compound and a cured product thereof, and an optical filter or sensor containing the resin composition.

Conventionally, various compounds that absorb light in the ultraviolet to purple region are known. As such compounds, for example, Patent Document 1 discloses a benzophenone-based compound, Patent Document 2 discloses a merocyanine-based compound, and Patent Document 3 discloses a triazine-based compound. Further, Patent Documents 4 and 5 disclose a resin composition containing a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber, and an optical film formed from the resin composition. There is.

JP-A-7-285927 Japanese Unexamined Patent Publication No. 2010-100787 Japanese Unexamined Patent Publication No. 2013-82707 Japanese Unexamined Patent Publication No. 2003-26942 Japanese Unexamined Patent Publication No. 2003-43259

The ultraviolet absorber may be blended with a resin and used as a resin composition, and the resin composition is used by molding it into various shapes depending on the application. The applications of resin molded products are expanding more and more, and the applications where heat resistance is required are also increasing. For example, when forming an optical filter from a transparent resin, the optical filter is formed by coating a resin composition on a transparent substrate and heating it, mounting it on an electronic component by solder reflow, or a dielectric by vapor deposition. A multilayer film may be formed, but if the resin composition contains an ultraviolet absorber, the ultraviolet absorber is sufficient so that the desired ultraviolet absorbing performance is exhibited even after undergoing these processes. It is required to have excellent heat resistance.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound showing an absorption peak in the ultraviolet to purple region and having excellent heat resistance, and a resin composition or an optical filter containing the compound. There is.

［式（１）中、Ｌは２価以上の連結基を表し、ａは２以上の整数を表し、Ａはそれぞれ独立して下記式（２）で示される基を表す。］

［式（２）中、
Ｒ¹はシアノ基、アシル基、カルボキシル基、カルボン酸エステル基、アミド基またはハロゲノアルキル基を表し、
Ｒ²は水素原子、シアノ基、アシル基、カルボキシル基、カルボン酸エステル基、アミド基、炭化水素基またはヘテロアリール基を表し、
Ｒ¹とＲ²がともにアシル基、カルボン酸エステル基またはアミド基である場合、Ｒ¹とＲ²は互いに連結して環を形成していてもよく、
Ｒ³は水素原子またはアルキル基を表し、
Ｒ⁴は水素原子、有機基または極性官能基を表し、複数のＲ⁴は互いに同一または異なっていてもよく、
Ｘは硫黄原子または酸素原子を表し、
＊は式（１）の連結基Ｌとの結合部位を表す。］
［２］前記Ｒ²が水素原子、シアノ基、アシル基、カルボン酸エステル基またはアミド基を表す［１］に記載のエチレン化合物。
［３］トルエン中で測定した波長３００ｎｍ〜６００ｎｍの範囲の吸収スペクトルにおいて、波長４２０ｎｍ以下に最大吸収ピークを有する［１］または［２］に記載のエチレン化合物。
［４］［１］〜［３］のいずれかに記載のエチレン化合物を含有することを特徴とする紫外線吸収剤。
［５］［１］〜［３］のいずれかに記載のエチレン化合物と樹脂成分とを含有することを特徴とする樹脂組成物。
［６］さらに近赤外線吸収色素および／または可視光吸収色素を含有する［５］に記載の樹脂組成物。
［７］さらにエポキシ基含有シランカップリング剤、その加水分解物、およびその加水分解縮合物よりなる群から選ばれる少なくとも１種を含有する［５］または［６］に記載の樹脂組成物。
［８］［５］〜［７］のいずれかに記載の樹脂組成物を硬化した硬化物。
［９］［５］〜［７］のいずれかに記載の樹脂組成物または［８］に記載の硬化物を含むことを特徴とする光学フィルター。
［１０］［９］に記載の光学フィルターを備えることを特徴とするセンサー。 The present invention includes the following inventions.
[1] An ethylene compound represented by the following formula (1).

[In the formula (1), L represents a linking group having a divalent value or more, a represents an integer of 2 or more, and A represents a group represented by the following formula (2) independently. ]

[In equation (2),
R ¹ represents a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group or a halogenoalkyl group.
R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group.
When ^{both R 1} and R ² are acyl groups, carboxylic acid ester groups or amide groups, R ¹ and R ² may be linked to each other to form a ring.
R ³ represents a hydrogen atom or an alkyl group
R ⁴ represents a hydrogen atom, an organic group or a polar functional group, and a plurality of R ^4s may be the same or different from each other.
X represents a sulfur atom or an oxygen atom,
* Represents the binding site with the linking group L of the formula (1). ]
[2] ^{The ethylene compound according to [1], wherein R 2} represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group or an amide group.
[3] The ethylene compound according to [1] or [2], which has a maximum absorption peak at a wavelength of 420 nm or less in an absorption spectrum in the wavelength range of 300 nm to 600 nm measured in toluene.
[4] An ultraviolet absorber containing the ethylene compound according to any one of [1] to [3].
[5] A resin composition containing the ethylene compound according to any one of [1] to [3] and a resin component.
[6] The resin composition according to [5], which further contains a near-infrared absorbing dye and / or a visible light absorbing dye.
[7] The resin composition according to [5] or [6], which further contains at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolyzed condensate thereof.
[8] A cured product obtained by curing the resin composition according to any one of [5] to [7].
[9] An optical filter comprising the resin composition according to any one of [5] to [7] or the cured product according to [8].
[10] A sensor comprising the optical filter according to [9].

The ethylene compound of the present invention shows an absorption peak in the ultraviolet to purple region and is excellent in heat resistance.

The absorption spectrum of ethylene compound 1 and comparative ethylene compound 1 obtained in Examples is shown in toluene. It represents the transmission spectrum of an optical filter formed from the epoxy resin composition 1 containing the ethylene compound 2 and the near-infrared absorbing dye obtained in the examples. The transmission spectrum of the optical filter formed from the epoxy resin composition 2 containing the ethylene compound 14 obtained in the examples is shown. It represents the transmission spectrum of an optical filter formed from the epoxy resin composition 3 containing the comparative ethylene compound 1 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the epoxy resin composition 4 containing the comparative ethylene compound 2 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the epoxy resin composition 5 containing the comparative ethylene compound 3 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the cycloolefin resin composition 1 containing the ethylene compound 1 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the cycloolefin resin composition 2 containing the comparative ethylene compound 1 and the near-infrared absorbing dye obtained in Examples. It represents the transmission spectrum of an optical filter formed from the cycloolefin resin composition 3 containing the comparative ethylene compound 3 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the polyarylate resin composition 1 containing the ethylene compound 12 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the polyarylate resin composition 2 containing the comparative ethylene compound 1 and the near-infrared absorbing dye obtained in the examples. It represents the transmission spectrum of an optical filter formed from the polyarylate resin composition 4 containing the ethylene compound 14 and the near-infrared absorbing dye obtained in the examples.

The ethylene compound of the present invention is represented by the following formula (1). The ethylene compound represented by the following formula (1) shows a sharp absorption peak in the ultraviolet to purple region and has excellent heat resistance. The ethylene compound of the present invention can function as an ultraviolet-absorbing ethylene compound.

In the formula (1), L represents a linking group having a divalent value or more, a represents an integer of 2 or more, and A represents a group represented by the following formula (2) independently.

In formula (2), R ¹ represents a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group or a halogenoalkyl group, and R ² is a hydrogen atom, a cyano group, an acyl group, a carboxyl group or a carboxylic acid ester. Representing a group, amide group, hydrocarbon group or heteroaryl group, where R ¹ and R ² are both acyl groups, carboxylic acid ester groups or amide groups, R ¹ and R ² are linked to each other to form a ring. R ³ may represent a hydrogen atom or an alkyl group, R ⁴ may represent a hydrogen atom, an organic group or a polar functional group, a plurality of R ^4s may be the same or different from each other, and X may be a sulfur atom or It represents an oxygen atom, and * represents a bonding site with the linking group L of the formula (1).

In the group A represented by the formula (2), the ^{ethylene structural part containing R 1} and R ² functions as a chromophore. In the formula (2), a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group, a halogenoalkyl group, a hydrocarbon group or a heteroaryl group is used as ^{R 1} and R ^2. In equation (2), R ¹ (or R ² ) may be in the cis position or in the trans position with respect to ^{R 3.}

The acyl groups (alkanoyl groups) of R ¹ and R ² include a methanoyl group, an etanoyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoil group, an octanoyl group, a nonanoyl group, a decanoyle group, an undecanoyl group, and a dodecanoyl group. , Tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyyl group, eikosanoyl group and the like. A part of the hydrogen atom of the acyl group may be substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms of the acyl group (the number of carbon atoms excluding the substituent) is preferably 2 to 21, more preferably 2 to 11, and even more preferably 2 to 6.

The carboxylic acid ester groups of R ¹ and R ² are represented by the formula: * -C (= O) -OR ¹¹ , where * represents the binding site of the ethylene double bond of the formula (2) to the carbon atom. .. In the formula, R ¹¹ represents a hydrocarbon group, preferably an alkyl group, an aryl group or an aralkyl group.

Alkyl groups of R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group and octyl group. Linear or branched alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group; cyclopropyl group , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and other cyclic (aliphatic) alkyl groups. In the alkyl group, a part of the hydrogen atom may be substituted with an alkoxy group, an aryl group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The number of carbon atoms of the alkyl group (the number of carbon atoms excluding the substituent) is preferably 1 to 20, and specifically, if it is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20 and more preferably 1 to 20. It is 10, more preferably 1 to 5, and if it is a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

Examples ^{of the aryl group of R 11} include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group and the like. A part of the hydrogen atom of the aryl group may be substituted with an alkyl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The number of carbon atoms of the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

Examples of the aralkyl group of R ¹¹ include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a naphthylmethyl group and the like. In the aryl group contained in the aralkyl group, a part of the hydrogen atom may be substituted with an alkyl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The carbon number of the aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, and more preferably 7 to 15.

The amide groups of R ¹ and R ² are represented by the formula: * -C (= O) -NR ¹² R ¹³ , where * represents the binding site of the ethylene double bond of the formula (2) to the carbon atom. In the formula, R ¹² represents a hydrogen atom or an alkyl group. R ¹³ represents a hydrocarbon group, preferably an alkyl group, an acyl group, an aryl group or an aralkyl group. Specific examples of the alkyl group of R ¹² and R ^{13 , the acyl group of R 13} and the aryl group and the aralkyl group are described above for ^{the alkyl group of R 11} , the aryl group, the aralkyl group, and the acyl group of ^{R 1} and R ^2. Is referenced.

When ^{both R 1} and R ² are acyl groups, R ¹ and R ² may be connected to each other to form a ring, and the ^{group formed from R 1 and R 2 in} this case is represented by the formula: The groups represented by * -C (= O) -R ^14- C (= O)-* are shown. In the formula, R ¹⁴ represents a linear or branched alkylene group, and * represents the binding site of the ethylene double bond of the formula (2) to a carbon atom. In the alkylene group, a part of the hydrogen atom may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The carbon number of the alkylene group of R ¹⁴ (the number of carbon atoms excluding the substituent) is preferably 2 to 10 and more preferably 3 to 8. Examples of the group (cyclic group) formed by linking the acyl groups of R ¹ and R ^{2 to each other include the group represented by the following formula (3-1).}

When ^{both R 1} and R ² are carboxylic acid ester groups, R ¹ and R ² may be connected to each other to form a ring, and the group formed from ^{R 1 and R 2 in this case is} Formula: The group represented by * -C (= O) -OR ^15- OC (= O)-* is shown. In the formula, R ¹⁵ represents a linear or branched alkylene group, and * represents the binding site of the ethylene double bond of the formula (2) to a carbon atom. In the alkylene group, a part of the hydrogen atom may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The carbon number of the alkylene group of R ¹⁵ (the number of carbon atoms excluding the substituent) is preferably 1 to 8, and more preferably 1 to 6. Examples of the group (cyclic group) formed by linking the carboxylic acid ester groups of R ¹ and R ^{2 to each other include the group represented by the following formula (3-2).}

When ^{both R 1} and R ² are amide groups, R ¹ and R ² may be connected to each other to form a ring, and the ^{group formed from R 1 and R 2 in} this case is represented by the formula: The groups represented by * -C (= O) -NR ^16- R ^17- NR ^18- C (= O)-* are shown. In the formula, R ¹⁶ and R ¹⁸ represent a hydrogen atom or a hydrocarbon group, R ¹⁷ represents a linear or branched alkylene group or a carbonyl group, and * represents an ethylene double bond of the formula (2). Represents the bond site of ethylene to a carbon atom. Preferred examples of the hydrocarbon group of R ¹⁶ and R ¹⁸ include an alkyl group, an aryl group or an aralkyl group. For specific examples of the alkyl group, aryl group and aralkyl group of ^{R 16} and R ¹⁸ , the above description of ^{the alkyl group, aryl group and aralkyl group of R 11 is referred to.} In ^{the alkylene group of R 17} , a part of the hydrogen atom may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The carbon number of the alkylene group of R ¹⁷ (the number of carbon atoms excluding the substituent) is preferably 1 to 8, and more preferably 1 to 6. Examples of the group (cyclic group) formed by linking the amide groups of R ¹ and R ² to each other include groups represented by the following formulas (3-3) and (3-4).

Examples of the halogenoalkyl group of R ¹ include those in which a part or all of the hydrogen atoms of the alkyl group of ^{R 11 described above are replaced with halogen atoms.} Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbon group of R ² include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. For a specific example of the aliphatic saturated hydrocarbon group, refer to the above description regarding the alkyl group ^{of R 11} , and for a specific example of the aliphatic unsaturated hydrocarbon group, the carbon-carbon single carbon of the alkyl group of ^{R 11 described above.} Examples include those in which a part of the bond is replaced with a double bond or a triple bond. For specific examples of the aromatic hydrocarbon group (aryl group), the above description regarding the aryl group ^{of R 11 is referred to.} As ^{the hydrocarbon group of R 2} , an aryl group is preferable.

The ^{heteroaryl group of R 2} includes thienyl group, thiopyranyl group, isothiochromenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyraridinyl group, pyrimidinyl group, pyridadinyl group, thiazolyl group, isothiazolyl group, furanyl group, Examples thereof include a pyranyl group. In the heteroaryl group, the carbon atom is preferably bonded to the carbon atom of the ethylene double bond of the formula (2), and the carbon atom adjacent to the hetero atom is the carbon atom of the ethylene double bond of the formula (2). It is more preferably bound to, which facilitates the synthesis of ethylene compounds. The heteroaryl group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

In the formula (2), R ² is preferably a hydrogen atom, a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group or an amide group, which facilitates effective absorption of light in the ultraviolet to purple region. Become. When you want to set the absorption peak of an ethylene compound to a longer wavelength side, for example, when you want to absorb light in the wavelength region of 350 nm to 420 nm instead of the complete ultraviolet region, R ² is not a hydrogen atom. Is preferable.

^{R 3} of the formula (2) represents a hydrogen atom or an alkyl group, and a specific example of the alkyl group is referred to in ^{the above description of the alkyl group of R 11.} The alkyl group of R ³ preferably has 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. A hydrogen atom is particularly preferable as ^{R 3.}

In the group A represented by the formula (2), the benzene ring bonded to the ethylene structure functions to donate an electron to the ethylene structure together with X (sulfur atom or oxygen atom) bonded to the benzene ring. Adjust the absorption wavelength of the chromophore of the ethylene structure so that it is in the ultraviolet to purple region. ^{R 4} bonded to the benzene ring represents a hydrogen atom, an organic group or a polar functional group, and a plurality of R ^4s may be the same or different from each other.

^{Examples of the organic group of R 4} of the formula (2) include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group and an aryloxycarbonyl. Examples thereof include a group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amide group, a sulfonamide group, a carboxy group (carboxylic acid group), a cyano group and the like. Examples ^{of the polar functional group of R 4} include a halogeno group, a hydroxyl group, a nitro group, a sulfo group (sulfonic acid group) and the like.

For specific examples of the alkyl group of ^{R 4} , refer to the above description of the alkyl group ^{of R 11.} The alkyl group of R ⁴ may have a substituent, and the substituent of the alkyl group includes an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group and a nitro group. Examples include an amino group and a sulfo group.

Specific examples of the alkyl group include an alkoxy group R ^4, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, the alkylsulfinyl group is described pertains to an alkyl group R ⁴ is referred to.

For specific examples of the aryl group and aralkyl group of ^{R 4} , the above description of the aryl group and aralkyl group ^{of R 11 is referred to.} The aryl group contained in the aryl group or aralkyl group of R ⁴ may have a substituent, and the substituents include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group and a cyano group. Group, nitro group, amino group, thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. Be done.

Aryloxy group R ^4, an arylthio group, an aryloxycarbonyl group, specific examples of the arylsulfonyl group, the aryl group contained in arylsulfinyl group, description of aryl group R ⁴ is referred to.

For specific examples of the heteroaryl group of ^{R 4} , refer to the above description of the heteroaryl group ^{of R 2.} The heteroaryl group may have a substituent, and the substituents of the heteroaryl group include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group and a nitro group. , Thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like.

The amino group of R ^{4 is represented by the formula: -NR 21} R ²² , and R ²¹ and R ²² are independently hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heteroaryl. Examples include those that are the basis. Refer to the above description for specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group, and as the alkenyl group and alkynyl group, a part of the carbon-carbon single bond of the alkyl group described above is double-bonded. Alternatively, substituents replaced with triple bonds may be mentioned, and these substituents may be partially substituted with halogen atoms. Further, R ²¹ and R ²² may be connected to each other to form a ring.

Examples ^{of the amide group of R 4} include those represented by the formula: -NH-C (= O) -R ²³ , in which R ²³ is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group and the like. For specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group, the above description is referred to, and a part of the hydrogen atom may be substituted with a halogen atom.

Examples of the sulfonamide group of R ⁴ include those represented by the formula: -NH-SO _2- R ²⁴ , in which R ²⁴ is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group and the like. For specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group, the above description is referred to, and a part of the hydrogen atom may be substituted with a halogen atom.

Examples of the halogeno group of R ⁴ include a fluoro group, a chloro group, a bromo group, an iodo group and the like.

The R ⁴ is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group and an arylthio group. For example, when R ⁴ is a nitrogen-containing substituent, it is ^{not so preferable because the substituent R 4} is decomposed by heating or reaction or changed to another structure, and the ethylene compound tends to be colored yellow or the like. .. From the viewpoint of enabling the ethylene compound to stably absorb light in the ultraviolet to purple region, R ⁴ is preferably a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms, and 1 to 1 3 is more preferable. ^{Among them, among the four} R 4s bonded to the benzene ring of the group A of the formula (2), it is preferable that two or more are hydrogen atoms, more preferably three or more are hydrogen atoms, and all four are all. It is particularly preferably a hydrogen atom.

X in the formula (2) represents a sulfur atom or an oxygen atom, which makes it easier for the ethylene compound to stably absorb light in the ultraviolet to purple region. From the viewpoint of effectively absorbing light in the UV region, X is preferably a sulfur atom.

In the group A represented by the formula (2), X may be bonded to the ethylene structure portion at the ortho position, may be bonded to the meta position, or may be bonded to the para position. From the viewpoint of ease of production of the ethylene compound, it is preferable that X is bonded to the ethylene structure at the para position.

In the formula (1), two or more groups A are bonded to the linking group L. By binding two or more groups A to the linking group L, the heat resistance of the ethylene compound can be enhanced. The two or more groups A attached to the linking group L may be the same or different from each other. The number a of the groups A bonded to the linking group L of the formula (1) is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less. From the viewpoint that an ethylene compound having high stability can be easily produced, a is more preferably 3 or less, and particularly preferably 2.

The linking group L is a divalent linking group such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, -SO _2- , -NH-; an alkyl group. Examples thereof include a methine group (-C <), a trivalent linking group such as -N <; a tetravalent linking group such as> C <; and a linking group combining these groups. The alkylene group may be linear, branched or cyclic. Further, the alkylene group and the arylene group may have a hydroxyl group and / or a thiol group.

Examples of the linking group L include groups represented by the following formulas (4-1) to (4-17). In formulas (4-1) to (4-17), * represents the binding site of group A. Two groups A are bonded to the connecting groups L of the formulas (4-1) to (4-9), and three groups A are attached to the connecting groups L of the formulas (4-10) to (4-13). 4 groups A are bonded to the connecting group L of the formulas (4-14) to (4-15), and 5 groups A are bonded to the linking group L of the formula (4-16). Six groups A are attached to -17).

From the viewpoint of enhancing the stability of the ethylene compound, the linking group L is an alkylene group in which a part of the hydrogen atom may be replaced with a hydroxyl group and / or a thiol group, and a part of the hydrogen atom is a hydroxyl group and / or a thiol group. An arylene group which may be replaced with, -O-, -S-, and a linking group in which these groups are combined are preferable (however, the ether bond and the thioether bond are not continuous). The carbon number (continuous carbon number) of the linear or branched alkylene group is preferably 6 or less, more preferably 4 or less, still more preferably 3 or less. If it is a cyclic alkylene group, the number of carbon atoms is preferably 4 or more, more preferably 5 or more, preferably 10 or less, and more preferably 8 or less. The number of carbon atoms of the arylene group is preferably 5 or more, more preferably 6 or more, preferably 10 or less, and more preferably 8 or less.

As the ethylene compound, the ethylene compound represented by the following formula (5) is particularly preferably shown. Such an ethylene compound has, for example, a peak having an absorption maximum in the wavelength range of 300 nm to 420 nm, can effectively absorb light in the ultraviolet to violet region, has excellent stability, and is easy to manufacture. .. In the following equation (5), ^{the description of R 1a} and R ^1b refers to the above description of R ¹ , the description of R ^2a and R ^2b refers to the above description of R ² , and the description of R ^3a and R ^3b . Refers to the description ^{of R 3} above, and ^{the description of X a} and X ^b refers to the description of X above.

The ethylene compound of the present invention has a maximum absorption at a wavelength of 420 nm or less in the absorption spectrum of a wavelength range of 300 nm to 600 nm (more preferably 300 nm to 700 nm, more preferably 300 nm to 800 nm) measured in toluene. It is preferable to have a peak. That is, the ethylene compound has a peak having an absorption maximum in the wavelength range of 300 nm to 420 nm when the absorption spectrum is measured in toluene, and the absorption maximum of the absorption peak has a maximum value in the wavelength range of 300 nm to 600 nm. Is preferable. If the ethylene compound exhibits such an absorption spectrum, it can effectively absorb light in the ultraviolet to violet region. The maximum wavelength of the absorption peak is more preferably 310 nm or more, further preferably 315 nm or more, further preferably 410 nm or less, and further preferably 400 nm or less.

When the absorbance of the maximum absorption peak at the maximum wavelength is 1, the ethylene compound preferably has a peak width of 100 nm or less at an absorbance of 0.5 of the absorption peak, more preferably 80 nm or less, and further 70 nm or less. preferable. If the ethylene compound shows such an absorption spectrum, it can selectively absorb light in the ultraviolet to violet region. The lower limit of the peak width is not particularly limited, but may be, for example, 20 nm or more, or 30 nm or more.

The ethylene compound preferably has an average absorbance in the wavelength range of 470 nm to 600 nm (preferably in the wavelength range of 450 nm to 700 nm) of 0.03 or less, where 1 is the absorbance of the maximum absorption peak at the maximum wavelength. 0.02 or less is more preferable, and 0.01 or less is further preferable, which can increase the light transmittance in a wide range of the visible light region.

The absorption spectrum is obtained by measuring the absorbance in a predetermined wavelength range at every measurement pitch of 1 nm. The value of the absorbance at the wavelength below the measurement pitch (1 nm) is calculated by linear interpolation from the measured value of the absorbance at the measurement pitch of 1 nm. The concentration of the ethylene compound in toluene is adjusted so that the absorbance at the maximum absorption peak of the maximum absorption peak is 1 ± 0.003. The average absorbance in the wavelength range of 470 nm to 600 nm is determined by averaging the absorbance values of 131 points measured at a pitch of 1 nm in the wavelength range of 470 nm to 600 nm.

Since the ethylene compound of the present invention can effectively absorb light in the ultraviolet to purple region, it can be suitably used as an ultraviolet absorber. The ethylene compound can be used by being dissolved or dispersed in any solvent (for example, water or an organic solvent). Therefore, the ultraviolet absorber may contain a solvent.

The ethylene compound contained in the ultraviolet absorber may be only one kind or two or more kinds. The ultraviolet absorber is a known ultraviolet absorber other than the ethylene compound of the present invention (for example, benzotriazole compound, benzophenone compound, salicylic acid compound, benzoxazineone compound, cyanoacrylate compound, benzoxazole compound, merocyanine). It may contain a system compound, a triazine compound, etc.).

The ethylene compound of the present invention can be produced, for example, according to the scheme shown below. In the following scheme, R ¹ to R ^3, X, L is the same meaning as in the formula (1), the preferred embodiments are also as described above. Y represents a halogen atom. In the following, the group R ⁴ is omitted, and an example in which a compound that gives a divalent linking group as the linking group L is used is shown.

First, by reacting the compound of the formula (6) that gives the precursor of the group A with the compound of the formula (7) that gives the linking group L, the precursor of the group A is bonded to both ends of the linking group L. The compound of (8) is obtained. The compound of the formula (6) is a halogenophenyl ketone compound or a halogenophenyl aldehyde compound, and the compound of the formula (6) may use only one kind or two or more kinds. The compound of formula (7) is a compound having a hydroxyl group and / or a thiol group. By reacting the compound of the formula (6) with the compound of the formula (7), the X (sulfur atom or oxygen atom) of the compound of the formula (7) is the carbon atom to which the halogen atom of the compound of the formula (6) is bonded. The compound of the formula (8) in which the precursor of the group A is bound to the linking group L is obtained.

Examples of the compound (7) include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanedithiol, 1,2-propanedithiol, 2-mercaptoethanol, thiodiglycol, and bis (2-mercaptoethyl) ether. , Bis (2-mercaptoethyl) sulfide, 1,3-bis (2-mercaptoethylthio) propane, cyclohexanediol, benzenediol, bisphenol A and other compounds that provide the divalent linking group L; glycerol, dimercaptols, Trivalent linking group L such as cyclohexanetril, benzenetriol, trimethylolpropanetrimercaptoaceto, trimethylolpropanetris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate. Compounds that give tetravalent linking group L such as erytritor, pentaerythritol tetrakis mercaptoaceto, pentaerythritol tetrakis (3-mercaptopropionate); compounds that give pentavalent linking group L such as ribitol; dipenta. Compounds and the like that provide a hexavalent linking group L, such as erythritol hexakis mercaptoaceto and dipentaerythritol hexakis (3-mercaptopropionate), can be used.

Then, the compound of the formula (8) and the compound of the formula (9) are subjected to a Knoevenagel condensation reaction to obtain the ethylene compound of the present invention of the formula (10). In the compound of formula (9), when ^{the methylene group between R 1} and R ² is sandwiched between a cyano group and / or a carbonyl group, the reactivity of the compound of formula (8) with the carbonyl group is particularly enhanced. Only one compound of the formula (9) may be used, or two or more compounds may be used.

Examples of compound (9) include acetonitrile, propionitrile, malononitrile, phenylacetic acid ester, cyanoacetic acid ester, malonic acid diester, 2-cyano-N, N-dimethylacetamide, N-methylacetamide, acetoacetanilide, N, N. , N', N'-tetramethylmalonamide, 1,3-cyclohexanedione, dimedone, meldrum acid, barbituric acid and the like can be used.

The above reaction is preferably carried out in the presence of a solvent. Examples of the solvent that can be used include chlorine-based hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene, xylene and trimethylbenzene; chlorine-based aromatics such as chlorotoluene and dichlorobenzene; tetrahydrofuran. Ethers such as (THF), dioxane, cyclopentylmethyl ether, diisopropyl ether, diethyl ether; nitriles such as acetonitrile, propionitrile, acrylonitrile, butyronitrile; alcohols such as methanol, ethanol, propanol, butanol; formic acid, acetic acid, Organic acids such as propionic acid; and the like. Only one of these solvents may be used, or two or more of these solvents may be used in combination.

In the above reaction, the reaction temperature may be appropriately set, for example, 0 ° C. or higher is preferable, 5 ° C. or higher is more preferable, 10 ° C. or higher is further preferable, 200 ° C. or lower is preferable, and 150 ° C. or lower is more preferable. The reaction may be carried out under reflux. The reaction time is not particularly limited and may be appropriately set according to the progress of the reaction. For example, 0.5 hours or more is preferable, 1 hour or more is more preferable, 48 hours or less is preferable, and 24 hours or less is preferable. More preferred. The atmosphere at the time of the reaction is preferably an inert gas (nitrogen, argon, etc.) atmosphere in the reaction for producing the compound of the formula (8).

The obtained ethylene compound can be appropriately purified by a known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation, recrystallization, and crystallization, if necessary.

The ethylene compound of the present invention can be mixed with a resin component to form a resin composition. Since the ethylene compound of the present invention has excellent heat resistance, the ultraviolet absorbing effect can be suitably exhibited even when it is blended with a thermoplastic resin and heat-molded, for example. Further, the resin composition containing the ethylene compound of the present invention can suppress deterioration caused by light in the ultraviolet to purple region, and is cured to form a resin molded body such as a film to obtain ultraviolet rays. It can be applied to an optical filter or the like that cuts light in the purple region. Furthermore, even if the resin composition or resin molded body is exposed to ultraviolet light during storage or during manufacturing / processing of an optical filter (for example, vapor deposition or mounting), the ultraviolet light is transmitted into the resin component or resin composition. It is possible to protect other components contained (such as a near-infrared absorbing dye described later) and suppress deterioration of these components.

The resin composition contains at least the ethylene compound of the present invention and a resin component. The ethylene compound contained in the resin composition may be only one kind or two or more kinds. The resin composition includes further ultraviolet absorbers (for example, benzotriazole-based compounds, benzophenone-based compounds, salicylic acid-based compounds, benzoxazine-based compounds, cyanoacrylate-based compounds, benzoxazole-based compounds, merocyanine-based compounds, and triazine-based compounds. Etc.) may be contained.

The content of the ethylene compound in the resin composition is preferably 0.01% by mass or more, preferably 0.03% by mass or more, based on 100% by mass of the solid content of the resin composition, from the viewpoint of exhibiting desired performance. Is more preferable, and 0.1% by mass or more is further preferable. Further, from the viewpoint of improving the moldability and film forming property of the resin composition, the content of the ethylene compound in the resin composition is preferably 25% by mass or less, preferably 20% by mass, based on 100% by mass of the solid content of the resin composition. % Or less is more preferable, and 15% by mass or less is further preferable. When the resin composition also contains other UV absorbers, the total content of these is preferably in the above range. The content of the other ultraviolet absorber is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the ethylene compound. The solid content of the resin composition means the amount of the resin composition excluding the solvent when the resin composition contains a solvent.

A known resin can be used as the resin component contained in the resin composition. As the resin component, one having high transparency and capable of dissolving or dispersing the ethylene compound of the present invention is preferable. When the resin composition also contains a near-infrared absorbing dye or a visible light absorbing dye as described later, the resin component is preferably one capable of dissolving or dispersing the dye. By selecting such a resin component, it is possible to achieve both high transmittance in the wavelength range to be transmitted and high absorption in the wavelength range to be blocked.

The resin component is not only a resin whose polymerization has been completed, but also a resin raw material (including a resin precursor, a raw material of the precursor, a monomer constituting the resin, etc.), and when molding a resin composition. It is also possible to use a resin which is incorporated into a resin by a polymerization reaction or a cross-linking reaction. In the present invention, any resin is included in the resin component. In the latter case, a part of the structure of the ethylene compound is caused by the unreactant, the reactive terminal functional group, the ionic group, the catalyst, the acid / basic group, etc., which are present in the reaction solution obtained by the polymerization reaction. Or it is possible that everything will be disassembled. Therefore, when there is such a concern, it is desirable to add an ethylene compound to the polymerized resin to form a resin composition.

As the resin component, it is preferable to use a highly transparent resin, whereby the characteristics of the ethylene compound contained in the resin composition can be suitably utilized. Examples of the resin component include (meth) acrylic resin, (meth) acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyolefin resin (for example, polyethylene resin and polypropylene resin), cycloolefin resin, and the like. Melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (eg nylon), aramid resin, polyimide resin, polyamideimide resin, alkyd resin, phenol resin, epoxy resin, polyester resin (eg polybutylene terephthalate (eg, polybutylene terephthalate) PBT) resin, polyethylene terephthalate (PET) resin, polyarylate resin, etc.), polysulfone resin, butyral resin, polycarbonate resin, polyether resin, ABS resin (acrylonitrile butadiene styrene resin), AS resin (acrylonitrile-styrene copolymer) , Silicone resin, modified silicone resin (eg, (meth) acrylic silicone resin, alkylpolysiloxane resin, silicone urethane resin, silicone polyester resin, silicone acrylic resin, etc.), fluororesin (eg, fluorinated aromatic polymer, etc.) Polytetrafluoroethylene (PTFE), perfluoroalkoxyfluororesin (PFA), fluorinated polyaryl ether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyether nitrile (FPEN) Etc.) etc. Among these, from the viewpoint of excellent transparency and heat resistance, polyimide resin, polyamideimide resin, (meth) acrylic resin, cycloolefin resin, epoxy resin, polyester resin, polyarylate resin, polyamide resin, polycarbonate resin, polysulfone. Resins and fluorinated aromatic polymers are preferable.

The polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain. For example, polycondensation of tetracarboxylic acid dianhydride and diamine is carried out to obtain polyamic acid, which is dehydrated and cyclized (imidized). ) Can be manufactured. As the polyimide resin, it is preferable to use an aromatic polyimide in which aromatic rings are linked by an imide bond. Polyimide resins include, for example, Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemicals, Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Meldin (registered trademark) manufactured by Coralvan, and Toray. TPS (registered trademark) TI3000 series manufactured by Plastic Seiko Co., Ltd. can be used.

The polyamide-imide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. As the polyamide-imide resin, for example, Toron (registered trademark) manufactured by Solvay Advanced Polymers, Vilomax (registered trademark) manufactured by Toyobo, TPS (registered trademark) TI5000 series manufactured by Toray Plastics Precision Precision Co., Ltd., and the like can be used.

The (meth) acrylic resin is a polymer having a repeating unit derived from (meth) acrylic acid or a derivative thereof, and for example, a repeating unit derived from a (meth) acrylic acid ester such as a poly (meth) acrylic acid ester resin. The resin to have is preferably used. The (meth) acrylic resin preferably has a ring structure in the main chain, for example, a carbonyl group-containing ring structure such as a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, and a maleimide ring structure; oxetane. Examples thereof include a carbonyl group-free ring structure such as a ring structure, an azetidine ring structure, a tetrahydrofuran ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, and a piperidine ring structure. The carbonyl group-containing ring structure also includes a structure containing a carbonyl group derivative group such as an imide group. Examples of the (meth) acrylic resin having a carbonyl group-containing ring structure are described in JP-A-2004-168882, JP-A-2008-179677, International Publication No. 2005/54311, JP-A-2007-31537 and the like. The ones described can be used.

The cycloolefin-based resin is a polymer obtained by using cycloolefin as at least a part of the monomer component and polymerizing the cycloolefin, and is not particularly limited as long as it has an alicyclic structure in a part of the main chain. Examples of cycloolefin resins include Topas (registered trademark) manufactured by Polyplastics, Appel (registered trademark) manufactured by Mitsui Chemicals, Zeonex (registered trademark) and Zeonoa (registered trademark) manufactured by Zeon Corporation, and JSR Corporation. Arton (registered trademark) manufactured by ZEON Corporation can be used.

Epoxy resin is a resin that can be cured by cross-linking an epoxy compound (prepolymer) in the presence of a curing agent or curing catalyst. Examples of the epoxy compound include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds and the like. For example, fluorene epoxy manufactured by Osaka Gas Chemical Co., Ltd. (Ogsol (registered trademark) PG-100). , Mitsubishi Chemicals, Inc. bisphenol A type epoxy compound (JER® 828EL), hydrogenated bisphenol A type epoxy compound (JER®, registered trademark) YX8000), Daicel Co., Ltd. alicyclic epoxy compound (EHPE (registered trademark)) ) 3150), a bifunctional alicyclic epoxy compound (celloxide (registered trademark) 2021P) and the like can be used.

The polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing a polyvalent carboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like. For example, OKP series manufactured by Osaka Gas Chemical Co., Ltd., TRN series manufactured by Teijin Co., Ltd., Theonex ( Registered trademark), Dupont's Rinite (registered trademark), Mitsubishi Chemical's Novapex (registered trademark), Mitsubishi Engineering Plastics' Novaduran (registered trademark), Toray's Lumirer (registered trademark), Trecon (registered trademark) Registered trademark), Elitel (registered trademark) manufactured by Unitica, etc. can be used.

The polyarylate resin is a polymer obtained by polycondensing a dihydric phenol compound and a dibasic acid (for example, an aromatic dicarboxylic acid such as phthalic acid), and has an aromatic ring and an ester bond in the repeating unit of the main chain. It has a repeating unit including and. As the polyarylate resin, for example, Vectran (registered trademark) manufactured by Kuraray, U polymer (registered trademark) manufactured by Unitika Ltd., Unifier (registered trademark), and the like can be used.

The polyamide resin is a polymer containing an amide bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in the main chain, and as such an amide resin, for example, nylon can be used. The polyamide resin may have an aromatic skeleton, and an aramid resin is known as such a polyamide resin. Aramid resin is preferably used because it has excellent heat resistance and strong mechanical strength. For example, Twaron (registered trademark) and Cornex (registered trademark) manufactured by Teijin, Kevlar (registered trademark) manufactured by DuPont, and Nomex. (Registered trademark) and the like can be used.

The polycarbonate resin is a polymer containing a carbonate group (-O- (C = O) -O-) as a repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) manufactured by Teijin, Upiron (registered trademark), Novarex (registered trademark), Zanter (registered trademark) manufactured by Mitsubishi Engineering Plastics, and SD Polyca manufactured by Sumika Stylon Polycarbonate. (Registered trademark) and the like can be used.

The polysulfone resin is a polymer having a repeating unit containing an aromatic ring, a sulfonyl group (−SO _{2−), and an oxygen atom.} As the polysulfone resin, for example, Sumika Excel (registered trademark) PES3600P or PES4100P manufactured by Sumitomo Chemical Co., Ltd., UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers, etc. can be used.

The fluorinated aromatic polymer is a repeat containing an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of ether bonds, ketone bonds, sulfone bonds, amide bonds, imide bonds and ester bonds. It is a polymer having a unit, and among these, a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferable. As the fluorinated aromatic polymer, for example, those described in JP-A-2008-181121 can be used.

The resin component preferably has high transparency, which facilitates suitable application of the resin composition to optical applications. As for the resin component, for example, the total light transmittance at a thickness of 0.1 mm is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more. The upper limit of the total light transmittance of the resin component is not particularly limited, and the total light transmittance may be 100% or less, but may be, for example, 95% or less. Total light transmittance is measured based on JIS K 7105.

The resin component preferably has a high glass transition temperature (Tg), which can enhance the heat resistance of the resin composition and various molded articles obtained from the resin composition. The glass transition temperature of the resin component is, for example, preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 130 ° C. or higher. The upper limit of the glass transition temperature of the resin component is not particularly limited, but is preferably 380 ° C. or lower, for example, from the viewpoint of ensuring the molding processability of the resin composition.

The resin composition may contain a near-infrared absorbing dye and / or a visible light absorbing dye. If the resin composition further contains a near-infrared absorbing dye and / or a visible light absorbing dye, an optical filter having light selective transmittance can be obtained from the resin composition. For example, if the resin composition contains the ethylene compound of the present invention and a near-infrared absorbing dye, the transmission of light in the ultraviolet to purple region and the red to near infrared region is suppressed, and the light in the visible light region is given priority. It can be used as a resin composition for a light selective transmission filter to be transmitted. When the resin composition contains the ethylene compound of the present invention and the visible light absorbing dye, it can be used as a resin composition for a coloring filter or a blue light reduction filter.

The near-infrared absorbing dye preferably has an absorption maximum in the wavelength range of 600 nm to 1100 nm. The near-infrared region dye more preferably has a peak having an absorption maximum in the wavelength range of 600 nm to 1100 nm in an absorption spectrum in the wavelength range of 450 nm to 1100 nm, and the absorption maximum of the absorption peak has a wavelength of 450 nm to 1100 nm. Take the maximum value in the range of. The absorption maximum wavelength is more preferably 630 nm or more, further preferably 660 nm or more, further preferably 680 nm or more, still more preferably 1000 nm or less, further preferably 900 nm or less, still more preferably 800 nm or less.

The visible light absorbing dye can be used without particular limitation as long as it has maximum absorption in the visible light region (for example, a wavelength range of more than 420 nm and less than 680 nm). Among them, as the visible light absorbing dye, it is preferable to use a dye having maximum absorption in a wavelength range of 500 nm or more and less than 680 nm, which has high luminosity factor.

The near-infrared absorbing dye and the visible light absorbing dye are particularly organic dyes, inorganic dyes, and organic-inorganic composite dyes (for example, organic compounds coordinated with metal atoms or ions). Not limited. Examples of the near-infrared absorbing dye and the visible light absorbing dye include a squarylium-based dye, a croconium-based dye, and copper (for example, Cu (II)) and zinc (for example, Zn (II)) as central metal ions. Cyclic tetrapyrrole pigments (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.), cyanine pigments, azo pigments, quinone pigments, xanthene pigments, indolin pigments, arylmethane pigments, etc. Examples thereof include pigments, quaterylene-based pigments, diimonium-based pigments, perylene-based pigments, quinacdrine-based pigments, oxazine-based pigments, dipyrromethene-based pigments, nickel complex-based pigments, and copper ion-based pigments. Only one kind of these dyes may be used, or two or more kinds may be used. Among them, at least one selected from cyanine-based dyes, squarylium compounds, croconium compounds, dipyrromethene-based dyes, and phthalocyanine compounds as near-infrared absorbing dyes and visible light absorbing dyes from the viewpoint of being able to effectively absorb light of a desired wavelength. It is preferable to use seeds. As the near-infrared absorbing dye, at least one selected from a squarylium compound, a croconium compound, and a phthalocyanine compound is used because it can effectively absorb light in the near-infrared region and increase the visible light transmittance. Is preferable.

When the near-infrared absorbing dye and / or the visible light absorbing dye is contained in the resin composition, the content of the near-infrared absorbing dye and the visible light absorbing dye in the resin composition is a resin from the viewpoint of exhibiting desired performance. The solid content of the composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.1% by mass or more, based on 100% by mass. Further, from the viewpoint of improving the moldability and film forming property of the resin composition, the content of the near-infrared absorbing dye and the visible light absorbing dye in the resin composition is 25% by mass in 100% by mass of the solid content of the resin composition. % Or less is preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable. The total content of the ethylene compound, the near-infrared absorbing dye, and the visible light absorbing dye (or the total content including other ultraviolet absorbers) is 30% by mass based on 100% by mass of the solid content of the resin composition. It is preferably 25% by mass or less, more preferably 20% by mass or less.

When the resin composition is used as a resin composition for a light selective transmission filter that preferentially transmits light in the visible light region, it is used as a near-infrared absorbing dye, for example, a squarylium compound represented by the following formula (11). Alternatively, it is preferable to use a croconium compound represented by the following formula (12). In the following formulas (11) and (12), R ^{21 to} R ²⁴ independently represent the groups represented by the following formulas (13) or (14).

In formula (13), ring P represents an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a fused ring containing these ring structures, and R ^{31 to} R ³³ are independent of each other. Thus, it represents a hydrogen atom, an organic group or a polar functional group, and R ³² and R ³³ may be linked to each other to form a ring. In formula (14), R ^{34 to} R ³⁸ independently represent a hydrogen atom, an organic group or a polar functional group, and R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , and R ³⁷ . Each of R ³⁸ may be connected to each other to form a ring. * Represents a binding site with a 4-membered ring in formula (11) or a 5-membered ring in formula (12).

For details of the organic groups and polar functional groups of R ^{31 to} R ³⁸ , refer to the above description of the organic groups and polar functional groups of ^{R 4.} When R ^{31 to} R ³⁸ are independent groups, it is preferable that R ^{31 to} R ³⁸ are independent hydrogen atoms, alkyl groups, aryl groups, aralkyl groups, amino groups, amide groups or hydroxy groups, respectively. Details of these groups are described for the above R ⁴ is referred to.

Examples of the ring structure formed from R ^{32 to} R ³⁸ include a hydrocarbon ring and a heterocycle, and these ring structures may or may not have aromaticity, but are non-aromatic. It is preferably a group hydrocarbon ring or a non-aromatic heterocycle. Examples of the non-aromatic hydrocarbon ring include cycloalkanes such as cyclopentane, cyclohexane and cycloheptane; cycloalkenes such as cyclopentene, cyclohexene and cyclohexadiene (for example, 1,3-cyclohexadiene), cycloheptene and cycloheptadiene. Can be mentioned. As the non-aromatic heterocycle, one or more carbon atoms constituting the ring of the hydrocarbon ring as described above are selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom). Examples include rings in which at least one or more atoms are replaced. Examples of the non-aromatic heterocycle include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholine ring, a hexamethyleneimine ring, a hexamethylene oxide ring, and a hexamethylene sulfide ring. Examples include the heptamethyleneimine ring.

In the group of formula (13), the ^{ring structure formed by connecting R 32} and R ³³ is preferably a 4- to 9-membered unsaturated hydrocarbon ring, among which cyclopentene, cyclohexene, cycloheptene, and cyclo. Cycloalkanemonoenes such as octene are more preferred. When the group of the formula (13) is configured in this way, the shoulder peak of the absorption waveform in the red to near infrared region is reduced, and the absorption peak becomes sharp.

Examples of the aromatic hydrocarbon ring of the ring P of the formula (13) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, a cyclotetradecaheptaene ring and the like. The aromatic hydrocarbon ring may have only one ring structure, or may be a condensation of two or more ring structures. The aromatic heterocycle of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom) and S (sulfur atom) in the ring structure and has aromaticity, for example. , Fran ring, thiophene ring, pyrol ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring and the like. The aromatic heterocycle may have only one ring structure or may be a condensed product of two or more ring structures. The fused ring containing these ring structures of ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused, and for example, an indole ring, an isoindole ring, a benzimidazole ring, and a quinoline ring. , Benzimidazole ring, acridine ring, xanthene ring, carbazole ring and the like. The absorption wavelength in the red to near infrared region can be easily adjusted by appropriately setting the π-conjugated system of the ring P.

Ring P may have a substituent, and examples of the substituent include the organic group and the polar functional group described above. When the ring P has a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. Ring P does not have to have a substituent.

For details of the squarylium compound and the croconium compound having the group of the formula (13), refer to the description of JP-A-2016-74649.

In the group represented by the formula (14), ^{it is preferable that R 35} and R ³⁶ are connected to form a ring, and further, R ³⁶ and R ³⁷ may be connected to form a ring. In this case, at least R ³⁴ and R ³⁸ are independent groups. If the group of the formula (14) is configured in this way, the absorption peak in the red to near infrared region becomes sharp. The ^{number of ring members of the ring structure formed of R 35} and R ³⁶ and the ring structure formed of R ³⁶ and R ³⁷ is preferably 5 or more, more preferably 6 or more, preferably 12 or less, and more preferably 10 or less. It is preferable, and 8 or less is more preferable.

In the group represented by the formula (14), or R ³⁶ is an amino group, or R ³⁶ is an amino group forms a ring with R ^35, form a ring further linked ³⁷ both R It is preferable to do so. In this case, the absorption maximum wavelength can be shifted to the long wavelength side (for example, 685 nm or more) to increase the transmittance of light in the red region and bring the color of the transmitted light closer to the actual one.

In the squarylium compound and the croconium compound having a group represented by the formula (14), the benzene rings on both sides of the squarylium skeleton or the croconium skeleton may be linked by a linking group. As such a compound, for example, a squarylium compound disclosed in Japanese Patent Application Laid-Open No. 2015-176046 is shown.

The resin composition is a silane coupling agent, a hydrolyzate of a silane coupling agent, and a hydrolyzed condensate of a silane coupling agent from the viewpoint of enhancing the adhesion when a resin layer is formed on a support (substrate). It is preferable to contain at least one selected from the above (hereinafter, these may be collectively referred to as "specific silane compound"). As the silane coupling agent used here, a silane coupling agent containing an epoxy group, an amino group, or a mercapto group is preferable, and an epoxy group-containing silane coupling agent is particularly preferable. When such a silane coupling agent is used, the adhesion of the resin layer to the support can be enhanced in combination with the inclusion of the ethylene compound in the resin composition.

As the epoxy group-containing silane coupling agent, a compound having an epoxy group and an alkoxysilyl group can be used. The epoxy group-containing silane coupling agent may contain only one epoxy group, may contain a plurality of epoxy groups, or may contain only one alkoxysilyl group, or may contain a plurality of epoxy silyl groups. You may.

When the epoxy group-containing silane coupling agent contains only one alkoxysilyl group, an alkoxysilane having an epoxy group represented by the following formula (15) is preferably used as the silane coupling agent.
SiR ⁴¹ _k R ⁴² _m (OR ⁴³ ) _n (OH) _4-kmn (15)

In formula (15), R ⁴¹ represents an epoxy group-containing group, R ⁴² and R ⁴³ each independently represent an alkyl group, k represents an integer of 1-3, and m represents an integer of 0-2. , N represent an integer of 1-3. When k is 2 or more, the plurality of R ^41s may be the same or different from each other, and when m is 2, the plurality of R ^42s may be the same or different from each other, and n is 2. In the above case, the plurality of OR ^43s may be the same or different from each other. R ⁴¹ , R ⁴² , OR ^43, and OH are groups that directly bond to Si, respectively.

In the formula (15), ^{the epoxy group-containing group of R 41} is not particularly limited as long as it contains an epoxy group, and examples thereof include a glycidoxy group-containing group and a cycloalkene oxide (alicyclic epoxy group) -containing group. The glycidoxy group and the cycloalkene oxide may be bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). R ⁴¹ preferably contains only one epoxy group. Examples of the epoxy group-containing group of R ⁴¹ include a glycidoxy group, a 3-glycidoxypropyl group, an 8- (glycidoxy) -n-octyl group, a 3,4-epoxycyclohexyl group, and a 2- (3,4-epoxycyclohexyl) group. Examples include an ethyl group. From the viewpoint of enhancing the adhesion of the resin layer to the support, ^{it is preferable that the epoxy group contained in R 41} is not too far from the silicon atom. For example, the glycidoxy group and the cycloalkene oxide are directly attached to the silicon atom. It is preferably bonded or bonded to a silicon atom via an alkylene group having 1 to 6 carbon atoms.

In the formula (15), ^{the alkyl groups of R 42} and R ⁴³ preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms. Preferred examples of R ⁴² include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Preferred examples of OR ⁴³ include a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.

In the formula (15), k is preferably 1 or 2, more preferably 1, which makes it easier to improve the adhesion of the resin layer to the support. Further, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

When the epoxy group-containing silane coupling agent contains a plurality of alkoxysilyl groups, the silane coupling agent is referred to as a polymer-type polyfunctional epoxy group-containing silane coupling agent (hereinafter, simply referred to as "polymer-type silane coupling agent"). In some cases) can be used. The polymer-type silane coupling agent has a structure in which an epoxy group-containing group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, and contains a plurality of alkoxysilyl groups in one molecule and also contains a plurality of epoxy groups. Can be done. The organic chain of the polymer-type silane coupling agent does not contain polysiloxane. Since the polymer-type silane coupling agent can have a plurality of alkoxysilyl groups and epoxy groups in one molecule in this way, many reaction points with the resin and the support are formed, and the resin layer adheres to the support. It can enhance the sex.

The hydrolyzate of the epoxy group-containing silane coupling agent can be obtained by converting the alkoxysilyl group contained in the silane coupling agent into a silanol group by hydrolysis. Further, the hydrolyzate of the epoxy group-containing silane coupling agent is formed by dehydrating and condensing the silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). Can be obtained by Usually, when a silane coupling agent is hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of silanol groups contained in the hydrolyzate also occurs, so that the hydrolysis condensation of the silane coupling agent occurs. Things can be easily obtained. The hydrolyzate of the silane coupling agent may be a dehydration condensate of the hydrolyzate of the same type of silane coupling agent, or may be a dehydration condensate of the hydrolyzate of a different type of silane coupling agent. ..

From the viewpoint of enhancing the adhesion of the resin layer to the support, the resin composition preferably contains at least a hydrolyzate or a hydrolyzed condensate of an epoxy group-containing silane coupling agent. More preferably, the resin composition contains a hydrolyzate or a hydrolyzed condensate of an alkoxysilane having an epoxy group (for example, an alkoxysilane represented by the above formula (15)), and more preferably an epoxy group. A hydrolyzed condensate of an alkoxysilane having (for example, an alkoxysilane represented by the above formula (15)) is included. The dehydration condensate in this case is, for example, equivalent to a pentamer when the weight average molecular weight of the specific silane compound contained in the resin composition is measured (however, it is assumed that all the alkoxy groups are hydroxyl groups). The molecular weight is preferably less than or equal to the molecular weight of, and more preferably less than or equal to the molecular weight equivalent to the tetramer. As a specific value of the weight average molecular weight, for example, 300 or more is preferable, 1000 or less is preferable, 800 or less is more preferable, and 600 or less is further preferable. The total content of the hydrolyzate and the hydrolyzed condensate of the epoxy group-containing silane coupling agent in 100% by mass of the characteristic silane compound is preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass. The above is more preferable.

The content of the specific silane compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, based on 100% by mass of the solid content of the resin composition. Further, 20% by mass or less is preferable, 10% by mass or less is more preferable, and 5% by mass or less is further preferable.

The content of the specific silane compound in the resin composition can be determined by gas chromatography or high performance liquid chromatography. The specific silane compound contained in the resin composition can be quantified for each type by gas chromatography or high performance liquid chromatography, and the content of the specific silane compound can be determined from the total. When a dehydrated condensate of a silane coupling agent (oligomer such as a dimer or a trimer) is contained, it may be used in combination with gel permeation chromatography analysis or the like to determine the existence form of the dehydrated condensate. it can. For example, in the case of hydrolyzing or further dehydrating and condensing an epoxy group-containing silane coupling agent, the residual amount after hydrolysis or further dehydration condensation is subtracted from the amount of the silane coupling agent used initially. The contents of the hydrolyzate and the hydrolyzed condensate can be determined.

The resin composition may contain a solvent. For example, when the resin composition is a paint-based resin composition, the inclusion of a solvent facilitates coating of the resin composition. The paint-based resin composition can be obtained, for example, by dissolving the ethylene compound in a solvent containing a resin component or by dispersing the ethylene compound in a solvent (dispersion medium) containing a resin component. The solvent may function as a solvent (solvent) for the ethylene compound or as a dispersion medium. Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; glycol derivatives such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and ethylene glycol ethyl ether acetate. Classes (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N, N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl-pyrrolidone (specifically, 1). Pyrrolidones such as −methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether and dibutyl ether; methanol , Ethyls such as ethanol, propanol and butanol; and the like. Only one of these solvents may be used, or two or more of these solvents may be used in combination.

The content of the solvent is preferably, for example, 50% by mass or more, more preferably 70% by mass or more, more preferably less than 100% by mass, and more preferably 95% by mass or less in 100% by mass of the resin composition. By adjusting the content of the solvent within such a range, it becomes easy to obtain a resin composition having a high ethylene compound concentration.

The resin composition may contain a surface conditioner, which suppresses appearance defects such as striations and dents in the resin layer when the resin composition is cured to form the resin layer. can do. The type of the surface conditioner is not particularly limited, and a siloxane-based surfactant, an acetylene glycol-based surfactant, a fluorine-based surfactant, an acrylic-based leveling agent, and the like can be used. As the surface conditioner, for example, BYK (registered trademark) series manufactured by Big Chemie, KF series manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be used.

The resin composition may contain a dispersant, which can stabilize the dispersibility of the ethylene compound and the like in the resin composition and suppress reaggregation. The type of dispersant is not particularly limited, and is EFKA series manufactured by Fuka Additives, BYK (registered trademark) series manufactured by Big Chemie, Solspers (registered trademark) series manufactured by Japan Lubrizol, and Disparon manufactured by Kusumoto Kasei. (Registered Trademark) Series, Ajinomoto Fine-Techno's Ajisper (Registered Trademark) Series, Shin-Etsu Chemical's KP Series, Kyoeisha Chemical's Polyflow Series, DIC's MegaFuck (Registered Trademark) Series, A Disper Aid series manufactured by San Nopco can be used.

The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity modifier, a defoaming agent, a preservative, a resistivity adjuster, and an adhesion improver, if necessary. ..

The resin composition can be made into a cured product by curing. The resin composition may be cured by a reaction of resin components (for example, a polymerization reaction or a cross-linking reaction), or may be cured by drying or heat-removing the solvent contained in the resin composition. May be good. Examples of such a resin composition include a thermoplastic resin composition that can be molded by injection molding, extrusion molding, or the like, a spin coating method, a solvent casting method, a roll coating method, a spray coating method, a bar coating method, and the like. A resin composition that has been made into a paint so that it can be coated by a dip coating method, a screen printing method, a flexographic printing method, an inkjet method, a slit coating method, or the like can be used. In the present invention, "curing" means a state in which the fluidity of the resin composition is reduced and the resin composition has substantially no fluidity. The "curing" includes a case where the resin composition is hardened by a reaction of the resin (for example, a polymerization reaction or a crosslinking reaction), a case where the solvent contained in the resin composition is removed, and the case where the resin composition is hardened.

When the resin composition is a thermoplastic resin composition, a cured product can be obtained by subjecting the resin composition to injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this method, a molded product is obtained by using a thermoplastic resin as a resin component, blending an ethylene compound with the thermoplastic resin, and heat-molding. For example, it is preferable to add an ethylene compound to the powder or pellet of the base resin, heat it to about 150 ° C. to 350 ° C. to dissolve it, and then mold it. The shape of the molded product is not particularly limited, but plate-like, sheet-like, granular, powder-like, lump-like, particle-aggregate-like, spherical, elliptical-spherical, lenticular, cubic, columnar, rod-like, and conical, Examples include a tubular shape, a needle shape, a fibrous shape, a hollow thread shape, and a porous shape. Further, when kneading the resin, an additive used for ordinary resin molding such as a plasticizer may be added.

When the resin composition is a paint-based resin composition, a liquid or paste-like resin composition containing an ethylene compound and a resin component is applied onto a base material (for example, a resin plate, a film, a glass plate, etc.). By working, a cured product having a thickness of 200 μm or less or a sheet having a thickness of more than 200 μm can be obtained. The cured product thus obtained can be peeled off from the base material and handled as a film or sheet, or can be handled integrally with the base material.

The cured product of the resin composition may be composed of a single resin layer (a layer formed by curing the resin composition), or may be composed of a plurality of resin layers. When the cured product is handled integrally with the base material, the cured product may be formed on only one side of the base material or on both sides. The cured product and the base material integrated with each other can also be formed by thermocompression bonding or chemically bonding the molded product formed from the resin composition to the base material.

Since the ethylene compound of the present invention has excellent heat resistance, even when it is blended with a thermoplastic resin and heat-molded, or when it is integrated with a support by thermocompression bonding or chemical bonding, the ultraviolet absorption effect is suitable. It can be demonstrated. In addition, resins that require a thermal curing reaction at high temperatures (for example, polyimide precursors, epoxy resins, acrylic resins, etc.) and resins that require drying at high temperatures (for example, resins containing high boiling point solvents and glass transition temperatures) Even when molded using a high resin), the excellent heat resistance of the ethylene compound makes it possible to suitably exert the ultraviolet absorbing effect.

The ultraviolet absorber or resin composition containing the ethylene compound of the present invention and its cured product are used for building materials such as coated glass, resin glass and interior / exterior materials, paints, adhesives, automobile parts, foods, pharmaceuticals, cosmetics and chemicals. Containers for storing, various films (protective film, optical film, retardation film, packaging film, agricultural film, etc.), various lenses (sunglasses, goggles, blue light cut glasses, medical protective glasses, etc.), For telephone line cable sheath materials used in electric wires, etc., members for irradiation devices that use ultraviolet light as a light source, fibers, display members, touch panels, optical filter members, optical sensor members, surface protection members such as cover glass and cover panels, and human bodies. It can be used for filter members that remove harmful ultraviolet rays, various sensor members (including malfunction prevention), lighting members, solar cell members, signs, signs, and the like.

The resin composition of the present invention can be preferably used as a resin composition for forming a filter used in various applications such as opt device applications, display device applications, mechanical parts, and electrical / electronic parts. The resin composition can be applied to an optical filter such as an ultraviolet cut filter or a light selective transmission filter that preferentially transmits light in the visible light region.

Image sensors such as mobile phone cameras, digital cameras, in-vehicle cameras, video cameras, and display elements (LEDs, etc.) usually use image sensors that convert the light of the subject into electrical signals and output it. Such an image sensor is provided with a light receiving element or lens such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor), and optical noise (an optical noise that hinders image processing or the like) for high performance. For example, a light selective transmission filter for removing ghosts and flares) is provided. Such a light selective transmission filter is usually provided with a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated, and the dielectric multilayer film is a high refractive index material layer. By adjusting the thickness of each layer of the low refractive index material layer, it is possible to cut the incident light in a desired wavelength range.

However, since the cut wavelength region or the transmission wavelength region of the dielectric multilayer film changes depending on the incident angle, when the incident angle changes from the vertical direction to the oblique direction, the cut wavelength region and the transmission wavelength region shift to the short wavelength side. Therefore, in the dielectric multilayer film, it may not be possible to sufficiently cut the light in the desired wavelength range with respect to the incident light in the oblique direction, or the light in the visible light region may also be cut to change the color. .. In particular, in recent years, there has been a strong demand for image pickup devices to be smaller and thinner, and the distance between the lens and the light receiving element is shortened accordingly. Therefore, the light receiving element needs to receive incident light from a more oblique direction. Sex comes out. In this case, since the incident angle dependence of the cut wavelength region and the transmission wavelength region becomes stronger, the light in the short wavelength region, that is, the light in the ultraviolet to purple region, which has hardly been affected in the past, is shifted to the short wavelength side. It will become apparent.

The resin composition of the present invention contains the ethylene compound described above, and since this ethylene compound shows a sharp absorption peak in the ultraviolet to purple region, the optical filter formed from the resin composition is ultraviolet to purple. The light in the region can be selectively absorbed, and the dependence on the incident angle on the short wavelength side of the visible light region can be reduced. Further, if the resin composition contains a near-infrared absorbing dye as well as an ethylene compound, the optical filter formed from the resin composition has an incident angle dependence on both the short wavelength side and the long wavelength side of the visible light region. Can be reduced. Moreover, since the ethylene compound contained in the optical filter has excellent heat resistance, decomposition and volatilization of the ethylene compound are suppressed even when the resin composition is heat-molded or heat-cured, or when a dielectric multilayer film is provided by vapor deposition. Therefore, the light in the ultraviolet to purple region can be effectively cut. Further, even if the optical filter is exposed to ultraviolet light during storage, manufacturing, and processing (for example, vapor deposition or mounting), deterioration of the resin component and the near-infrared absorbing dye due to the ultraviolet light can be suppressed.

The optical filter may be formed from a single or a plurality of resin layers, or may be formed integrally with a support. The filter integrated with the support is, for example, when the resin composition has another layer such as a binder layer between the support surface (or the support and the resin layer, the surface of the other layer). ) Can be formed by applying it to) by a spin coating method or a solvent casting method, and drying or curing it. Further, the filter may be formed by thermocompression bonding a planar molded product formed from the resin composition to the support.

The resin layer formed from the resin composition may be provided on only one side of the support, or may be provided on both sides. The thickness of the resin layer is not particularly limited, but from the viewpoint of ensuring the desired near-infrared ray cutting performance, for example, 0.5 μm or more is preferable, 1 μm or more is more preferable, 2 μm or more is further preferable, and 1 mm or less is preferable, and 500 μm. The following is more preferable, and 200 μm or less is further preferable. When the resin layer is formed by applying a paint-based resin composition on the support, the strength of the filter can be ensured by the support, so that the thickness of the resin layer should be further reduced. Can be done. When the resin layer is formed on the support, the thickness of the resin layer is, for example, preferably 50 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less.

As the support, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. As the resin plate or resin film used for the support, for example, those formed from the resin components described above are preferably used. From the viewpoint of increasing the heat resistance of the optical filter, it is preferable to use a glass substrate as the support, and the optical filter formed in this way can be mounted on an electronic component by, for example, solder reflow. Further, since the glass substrate is less likely to crack or warp even when exposed to a high temperature, it becomes easy to secure the adhesiveness with the resin layer. When a glass substrate is used as the support, a binder layer formed of, for example, a silane coupling agent may be provided between the support and the resin layer, thereby improving the adhesion between the resin layer and the glass substrate. Can be done.

The thickness of the support (board) is preferably 0.05 mm or more, more preferably 0.1 mm or more, and preferably 0.4 mm or less, preferably 0.3 mm, from the viewpoint of ensuring strength. The following is more preferable.

On the resin layer formed from the resin composition, a protective layer made of the same or different resin as the resin layer may be laminated as the second resin layer. By providing the protective layer, the durability (decomposition resistance) of the ethylene compound contained in the resin layer can be enhanced. The protective layer may be provided on only one side of the resin layer, or may be provided on both sides. When the resin layer is provided on the support, it is preferable that the protective layer is provided on the surface of the resin layer opposite to the support.

The optical filter has a layer having antireflection and antiglare properties (antireflection film) to reduce reflection of fluorescent lamps, a layer having scratch prevention performance, a transparent base material having other functions, and the like. You may. The optical filter may have an ultraviolet reflective film or a near infrared reflective film on the resin layer. The ultraviolet reflective film and the near infrared reflective film are preferably provided on the light receiving side of the resin layer. If the optical filter is provided with an ultraviolet reflecting film or a near-infrared reflecting film, ultraviolet rays and near-infrared rays can be further cut from the transmitted light of the optical filter. The ultraviolet reflective film and the near-infrared reflecting film may have one ultraviolet reflecting function and one near infrared reflecting function.

The ultraviolet reflective film, the near infrared reflective film, and the antireflection film (visible light antireflection film) can be composed of a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. Therefore, when imparting such a function to the optical filter, it is preferable that the optical filter has a dielectric multilayer film. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index in the range of 1.7 to 2.5 is usually selected. Examples of the material constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide and bismuth oxide; silicon nitride. Nitridees such as; the oxides and mixtures of the nitrides, and those obtained by doping them with metals such as aluminum and copper and carbon (for example, tin-doped indium oxide (ITO), antimonated tin oxide (ATO)) and the like. Be done. As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index in the range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride, and the like.

The optical filter may also have an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed.

The thickness of the optical filter is preferably 1 mm or less, for example. Thereby, for example, it is possible to sufficiently meet the demand for miniaturization of the image sensor. The thickness of the optical filter is more preferably 500 μm or less, still more preferably 300 μm or less, even more preferably 150 μm or less, still more preferably 30 μm or more, still more preferably 50 μm or more.

The optical filter can be used as one of the constituent members of a sensor such as an image sensor (imaging element), an illuminance sensor, and a proximity sensor. For example, an image sensor is used as an electronic component that converts the light of a subject into an electric signal or the like and outputs it, and examples thereof include a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor). The image sensor can be used for a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, a display element (LED, etc.) and the like. The sensor includes one or more of the above optical filters, and may have other filters (for example, a visible light cut filter, an infrared cut filter, an ultraviolet cut filter, etc.) and a lens, if necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples, and is carried out with appropriate modifications to the extent that it can be adapted to the gist of the above and the following. It is also possible, all of which are within the technical scope of the invention.

(1) Synthesis of compound (1-1) Synthesis example 1: Synthesis of ethylene compound 4.98 g (0.039 mol) of 4-fluorobenzaldehyde and bis (2-mercaptoethyl) ether in a 200 mL 4-neck flask. 72 g (0.020 mol), 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile were charged and reacted at 60 ° C. for 12 hours while stirring with a stirring blade under nitrogen flow (10 mL / min). After completion of the reaction, the insoluble matter was filtered off by vacuum filtration, and then the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL 4-neck flask, 5.19 g (0.079 mol) of malononitrile, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added thereto, and the mixture was reacted under reflux conditions for 4 hours. .. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 6.2 g of ethylene compound 1. The yield with respect to 4-fluorobenzaldehyde was 71.3 mol%. The structure of the obtained compound was specified by taking about 5 mg, diluting it in a predetermined amount of deuterated solvent (deuterated chloroform or deuterated dimethylsulfoxide), and ^{measuring 1} H-NMR.

(1-2) Synthesis Example 2: Synthesis of Ethylene Compound 2 Ethylene compound 2 shown in Table 1 was prepared by the same procedure as in Synthesis Example 1 except that methyl cyanoacetate was used instead of malononitrile in Synthesis Example 1. 9.9 g was obtained. The yield with respect to 4-fluorobenzaldehyde was 87.4 mol%.

(1-3) Synthesis Example 3: Synthesis of Ethylene Compound 3 Ethylene compound 3 shown in Table 1 was prepared by the same procedure as in Synthesis Example 1 except that dimethyl malonate was used instead of malononitrile in Synthesis Example 1. I got 0.4g. The yield with respect to 4-fluorobenzaldehyde was 35.7 mol%.

(1-4) Synthesis Example 4: Synthesis of Ethylene Compound 4 The ethylene compound 4 shown in Table 1 was subjected to the same procedure as in Synthesis Example 3 except that an equal volume of acetic acid was added to piperidine in Synthesis Example 3. Was obtained in an amount of 6.1 g. The yield with respect to 4-fluorobenzaldehyde was 80.0 mol%.

(1-5) Synthesis Example 5: Synthesis of Ethylene Compound 5 Ethylene compound 5 shown in Table 1 was prepared in the same procedure as in Synthesis Example 1 except that butyl cyanoacetate was used instead of malononitrile in Synthesis Example 1. 0.3 g was obtained. The yield with respect to 4-fluorobenzaldehyde was 14.8 mol%.

(1-6) Synthesis Example 6: Synthesis of Ethylene Compound 6 Ethylene compound 6 shown in Table 1 was prepared by the same procedure as in Synthesis Example 1 except that isobutyl cyanoacetate was used instead of malononitrile in Synthesis Example 1. 1.6 g was obtained. The yield with respect to 4-fluorobenzaldehyde was 18.1 mol%.

(1-7) Synthesis Example 7: Synthesis of Ethylene Compound 7 The ethylene compound 7 shown in Table 1 was subjected to the same procedure as in Synthesis Example 1 except that 2-ethylhexyl cyanoacetic acid was used instead of malononitrile in Synthesis Example 1. Was obtained in an amount of 2.5 g. The yield with respect to 4-fluorobenzaldehyde was 24.2 mol%.

(1-8) Synthesis Example 8: Synthesis of ethylene compound 8 Ethylene compound 8 shown in Table 1 was prepared in the same procedure as in Synthesis Example 1 except that meldrum's acid was used instead of malononitrile in Synthesis Example 1. I got 8g. The yield with respect to 4-fluorobenzaldehyde was 49.1 mol%.

(1-9) Synthesis Example 9: Synthesis of Ethylene Compound 9 Table 2 shows the same procedure as in Synthesis Example 1 except that 1,3-dimethylbarbituric acid was used instead of malononitrile in Synthesis Example 1. 7.3 g of ethylene compound 9 was obtained. The yield with respect to 4-fluorobenzaldehyde was 58.9 mol%.

(1-10) Synthesis Example 10: Synthesis of Ethylene Compound 10 Synthesis Example 2 except that ethylene glycol bis (2-mercaptoethyl) ether was used instead of bis (2-mercaptoethyl) ether in Synthesis Example 2. 3.8 g of ethylene compound 10 shown in Table 2 was obtained by the same procedure as above. The yield with respect to 4-fluorobenzaldehyde was 75.6 mol%.

(1-11) Synthesis Example 11: Synthesis of ethylene compound 11 In Synthesis Example 3, the same as Synthesis Example 3 except that ethylene glycol bis (2-mercaptoethyl) ether was used instead of bis (2-mercaptoethyl) ether. 1.1 g of ethylene compound 11 shown in Table 2 was obtained by the same procedure. The yield with respect to 4-fluorobenzaldehyde was 25.2 mol%.

(1-12) Synthesis Example 12: Synthesis of ethylene compound 12 Synthesis Example 6 except that ethylene glycol bis (2-mercaptoethyl) ether was used instead of bis (2-mercaptoethyl) ether in Synthesis Example 6. 4.6 g of ethylene compound 12 shown in Table 2 was obtained by the same procedure as above. The yield with respect to 4-fluorobenzaldehyde was 79.6 mol%.

(1-13) Synthesis Example 13: Synthesis of ethylene compound 13 In a 200 mL four-necked flask, 4.61 g (0.0328 mol) of 4-chlorobenzaldehyde and 2.92 g (0.22 g (0.23 mercaptoethyl) ether of ethylene glycol bis) are used. 016 mol), 0.63 g (0.048 mol) of potassium carbonate, 0.52 g (0.0016 mol) of tetrabutylammonium bromide, and 30.11 g of acetonitrile were charged and stirred under nitrogen flow (10 mL / min) using a stirring blade. The reaction was carried out at 75 ° C. for 6 hours. After completion of the reaction, the insoluble matter was filtered off by vacuum filtration, and then the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL 4-neck flask, 7.37 g (0.071 mol) of malonic acid, 0.61 g (0.007 mol) of piperidine, and 15 g of pyridine were added thereto, and the mixture was reacted under reflux conditions for 2 hours. It was. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 7.0 g of ethylene compound 13 shown in Table 2. The yield with respect to 4-chlorobenzaldehyde was 92.0 mol%. The structure of the obtained compound was specified by taking about 5 mg, diluting it in a predetermined amount of deuterated solvent (deuterated chloroform or deuterated dimethylsulfoxide), and ^{measuring 1} H-NMR.

(1-14) Synthesis Example 14: Synthesis of ethylene compound 14. In a 200 mL four-necked flask, 4.75 g (0.010 mol) of the ethylene compound 13 obtained in Synthesis Example 13 and p-toluenesulfonic acid monohydrate 0.19 g (0.001 mol) and 80 g of 1-butanol were charged and reacted under reflux conditions under reflux conditions under nitrogen flow (10 mL / min) while stirring with a stirring blade. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 4.9 g of ethylene compound 14 shown in Table 2. The yield with respect to 4-chlorobenzaldehyde was 83.5 mol%. The structure of the obtained compound was specified by taking about 5 mg, diluting it in a predetermined amount of deuterated solvent (deuterated chloroform or deuterated dimethylsulfoxide), and ^{measuring 1} H-NMR.

(1-15) Synthesis Example 15: Synthesis of Comparative Ethylene Compound 1 In a 200 mL 4-neck flask, 3.85 g (0.031 mol) of 4-fluorobenzaldehyde, 5.02 g (0.031 mol) of 4-chlorobenzyl mercaptan, and carbonate. 8.57 g (0.062 mol) of potassium and 36 g of acetonitrile were charged and reacted at 60 ° C. for 12 hours under nitrogen flow (10 mL / min) while stirring using a stirring blade. After completion of the reaction, the insoluble matter was filtered off by vacuum filtration, and then the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL 4-neck flask, 4.10 g (0.062 mol) of malononitrile, 2.64 g (0.031 mol) of piperidine, and 41 g of methanol were added thereto, and the mixture was reacted under reflux conditions for 4 hours. .. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 8.9 g of Comparative Ethylene Compound 1 shown in Table 2. The yield with respect to 4-fluorobenzaldehyde was 92.6 mol%.

(1-16) Synthesis Example 16: Synthesis of Comparative Ethylene Compound 2 Comparative ethylene compound 2 shown in Table 2 was subjected to the same procedure as in Synthesis Example 15 except that methyl cyanoacetate was used instead of malononitrile in Synthesis Example 15. 1.7 g was obtained. The yield with respect to 4-fluorobenzaldehyde was 29.9 mol%.

(1-17) Synthesis Example 17: Synthesis of Comparative Ethylene Compound 3 Table 2 follows the same procedure as in Synthesis Example 15 except that 4-isopropylbenzenethiol was used instead of 4-chlorobenzyl mercaptan in Synthesis Example 15. 3.5 g of the comparative ethylene compound 3 shown in the above was obtained. The yield with respect to 4-fluorobenzaldehyde was 71.9 mol%.

(2) Preparation of Epoxy Resin (EP Resin) Composition (2-1) Preparation of Curing Catalyst TPB (tris (pentafluorophenyl) borane) content 7 according to the synthesis method described in International Publication No. 1997/031924. 25 g of Isopar® E solution manufactured by Ando Parachemy Co., Ltd. was prepared. Water was added dropwise to this solution at 60 ° C. to precipitate white crystals, which were cooled to room temperature, suction filtered, and washed with n-heptane. The obtained cake was dried under reduced pressure at 60 ° C. to obtain 18.7 g of a TPB / water complex (TPB-containing powder) as white crystals. This complex had a water content of 9.2% (Karl Fischer titer) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the dried complex, but no peak other than TPB was detected. 2.0 g of the obtained TPB / water complex and 1.1 g of toluene were mixed and mixed at room temperature for 10 minutes. Then, 2.6 g of a 2 mol / L ammonia / ethanol solution was added and mixed at room temperature for 60 minutes to prepare a uniform solution of the TPB catalyst. This was used as a cationic curing catalyst.

(2-2) Preparation of silane hydrolyzate solution 3-glycidoxypropyltrimethoxysilane (OFS-6040, manufactured by Toray Dow Corning) 24.7 parts by mass, 2-propanol 32.1 parts by mass and distilled water 3.4 parts by mass was blended and mixed uniformly at 25 ° C. To this, 1.54 parts by mass of formic acid was added and mixed for 90 minutes to proceed with the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane to obtain a silane hydrolyzate solution.

(2-3) Preparation of Epoxy Resin Composition 1 As an epoxy resin, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Co., Ltd., 100 parts by mass of EHPE3150), 150 parts by mass of toluene and 75 parts by mass of o-xylene as a solvent, and the squarylium compound A shown below as a near-infrared absorbing dye (described in Example 1-18 of JP-A-2016-74649). 8.9 parts by mass, 8.4 parts by mass of the ethylene compound 2 obtained in Synthesis Example 2, and 0.3 parts by mass of BYK-306 (polyether-modified polydimethylsiloxane) manufactured by Big Chemie Co., Ltd. as a surface conditioner were blended. The mixture was uniformly mixed at 40 ° C. After lowering the temperature of the obtained mixture to 25 ° C., 2.5 parts by mass of the cation curing catalyst obtained above and 10 parts by mass of the silane hydrolyzate solution were added and mixed uniformly, and this was mixed with a filter having a pore size of 0.45 μm. Foreign matter was removed by filtration through a non-aqueous 13N) manufactured by GL Science Co., Ltd. to obtain an epoxy resin composition 1.

(2-4) Preparation of Epoxy Resin Composition 2 Except that the near-infrared absorbing dye was not used and the ethylene compound 14 was used instead of the ethylene compound 2 in the above preparation example of the epoxy resin composition 1. , An epoxy resin composition 2 was obtained by the same procedure.

(2-5) Preparation of Epoxy Resin Composition 3 The epoxy resin composition 3 is prepared by the same procedure except that the comparative ethylene compound 1 is used instead of the ethylene compound 2 in the above preparation example of the epoxy resin composition 1. Got

(2-6) Preparation of Epoxy Resin Composition 4 The epoxy resin composition 4 is prepared by the same procedure except that the comparative ethylene compound 2 is used instead of the ethylene compound 2 in the above preparation example of the epoxy resin composition 1. Got

(2-7) Preparation of Epoxy Resin Composition 5 The epoxy resin composition 5 is prepared by the same procedure except that the comparative ethylene compound 3 is used instead of the ethylene compound 2 in the above preparation example of the epoxy resin composition 1. Got

(3) Preparation of Cycloolefin Resin (COP Resin) Composition (3-1) Preparation of Cycloolefin Resin Composition 1 Cycloolefin Resin (manufactured by Polyplastics, TOPAS® 5013) 126 parts by mass Was added to a mixed solvent of 435 parts by mass of toluene and 439 parts by mass of o-xylene, 10 parts by mass of the above squarylium compound A, and 8.4 parts by mass of the ethylene compound 1 obtained in Synthesis Example 1 for surface preparation. BYK-330 (polyether-modified polydimethylsiloxane) manufactured by Big Chemie Co., Ltd. was added as an agent by 0.52 parts by mass and mixed uniformly to obtain a cycloolefin resin composition 1.

(3-2) Preparation of Cycloolefin Resin Composition 2 Cyclo by the same procedure except that the comparative ethylene compound 1 was used instead of the ethylene compound 1 in the above preparation example of the cycloolefin resin composition 1. An olefin resin composition 2 was obtained.

(3-3) Preparation of Cycloolefin Resin Composition 3 Cyclo by the same procedure except that the comparative ethylene compound 3 was used instead of the ethylene compound 1 in the above preparation example of the cycloolefin resin composition 1. An olefin resin composition 3 was obtained.

(4) Preparation of polyarylate resin (PAR resin) composition (4-1) Synthesis of polyarylate resin 2,2'-bis (4-hydroxyphenyl) propane in a reaction vessel having a capacity of 2 liters equipped with a stirring blade. 10.01 g (0.044 mol), 3.59 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water were charged and dissolved, and then 0.89 g (0.009 mol) of triethylamine was added and dissolved. .. A solution prepared by dissolving 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride in 500 g of methylene chloride was placed in a dropping funnel, and this was attached to the reaction vessel. The solution in the reaction vessel was stirred while maintaining the temperature at 20 ° C., and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution prepared by dissolving 0.71 g (0.005 mol) of benzoyl chloride in 10 g of methylene chloride was added thereto, and the mixture was stirred for 60 minutes. An aqueous acetic acid solution was added to the obtained reaction solution for neutralization to bring the pH of the aqueous phase to 7, and then the oil phase and the aqueous phase were separated using a separatory funnel. The obtained oil phase was added dropwise to methanol under stirring to reprecipitate the polymer, and the precipitate was recovered by filtration and dried in an oven at 80 ° C. to obtain a white solid polyarylate resin. The yield was 11.5 g. The weight average molecular weight (Mw) of the obtained polyarylate resin was 33,780, and the number average molecular weight (Mn) was 8,130. The weight average molecular weight and the number average molecular weight of the polyarylate resin are polystyrene-equivalent values obtained by gel permeation chromatography measurement.

(4-2) Preparation of Polyallylate Resin Composition 1 100 parts by mass of the polyallylate resin obtained above was added to a mixed solvent of 283 parts by mass of toluene and 283 parts by mass of o-xylene, and further added thereto as a near-infrared absorbing dye. 3.3 parts by mass of the above squarylium compound A and 1.1 parts by mass of the squarylium compound B shown below, 8 parts by mass of the ethylene compound 12 obtained in Synthesis Example 12, BYK-330 manufactured by Big Chemie as a surface conditioner. (Polyether-modified polydimethylsiloxane) was added in an amount of 0.52 parts by mass and mixed uniformly to obtain a polyarylate resin composition 1.

(4-3) Preparation of Polyallylate Resin Composition 2 100 parts by mass of the polyallylate resin obtained above is added to a mixed solvent of 283 parts by mass of toluene and 283 parts by mass of o-xylene, and the above squarylium compound A is further added thereto. 3.3 parts by mass, 8.4 parts by mass of the comparative ethylene compound 1 obtained in Synthesis Example 13, and 0.52 parts by mass of BYK-330 (polyether-modified polydimethylsiloxane) manufactured by Big Chemie as a surface conditioner. The mixture was uniformly mixed to obtain a polyarylate resin composition 2.

(4-4) Preparation of Polyarylate Resin Composition 3 The polyarylate resin composition 1 obtained above and the hydrolyzed solution of the epoxy group-containing silane coupling agent are mixed in a mass ratio of the former: the latter = 99: 1. The polyarylate resin composition 3 was obtained by uniformly mixing at 25 ° C. and filtering this with a filter having a pore size of 0.1 μm (manufactured by GL Science, non-aqueous 13N) to remove foreign substances. The hydrolyzed solution of the epoxy group-containing silane coupling agent was 34.7 parts by mass of 3-glycidoxypropyltrimethoxysilane (OFS-6040 manufactured by Toray Dowcorning Co., Ltd.) and 32.1 parts by mass of 2-propanol. And 3.4 parts by mass of distilled water were mixed and mixed uniformly at 25 ° C., then 1.54 parts by mass of formic acid was added and mixed for 90 minutes to hydrolyze 3-glycidoxypropyltrimethoxysilane. Prepared by advancing.

(4-5) Preparation of Polyallylate Resin Composition 4 In the above preparation example of the polyallylate resin composition 3, the squarylium compound C (Tetrahedron Letters) shown below is used as a visible light absorbing dye instead of the squarylium compound A and the squarylium compound B. , Vol.40, pp.4067-4068 (1999) except that the product 3a) disclosed in Table 1 was used and the ethylene compound 14 obtained in Synthesis Example 14 was used instead of the ethylene compound 12. Obtained the polyallylate resin composition 4 by the same procedure as in the preparation example of the polyallylate resin composition 3.

(4-6) Preparation of Polyallylate Resin Composition 5 The polyallylate resin composition 5 was prepared by the same procedure except that the squarylium compound A and the squarylium compound B were not used in the preparation example of the polyallylate resin composition 3. Got

(4-7) Preparation of Polyarylate Resin Composition 6 In the preparation example of the polyarylate resin composition 5, instead of the hydrolyzed solution of the epoxy group-containing silane coupling agent, 3-glycidoxypropyltrimethoxysilane (Toray)・ Except for using a mixed solution containing 24.7 parts by mass of OFS-6040, manufactured by Dow Corning, 32.1 parts by mass of 2-propanol, 3.4 parts by mass of distilled water, and 1.54 parts by mass of formic acid. , Polyarylate resin composition 6 was obtained by the same procedure.

(4-8) Preparation of Polyarylate Resin Composition 7 A polyarylate resin composition 7 was obtained by the same procedure except that the squalylium compound C was not used in the preparation example of the polyarylate resin composition 4.

(4-9) Preparation of Polyarylate Resin Composition 8 A polyarylate resin composition 8 was obtained by the same procedure except that ethylene compound 12 was not used in the preparation example of the polyarylate resin composition 3.

(5) Preparation of Optical Filter After 2 cc of each of the resin compositions obtained above was dropped on a glass substrate (D263Teco manufactured by Schott), a spin coater (1HD7 manufactured by Mikasa) was used. The resin composition was formed on a glass substrate at 1600 rotations over 2 seconds, held at that rotation speed for 20 seconds, and then at 0 rotations over 0.2 seconds. The glass substrate on which the resin composition was formed was initially dried at 100 ° C. for 3 minutes using a precision thermostat (manufactured by Yamato Scientific Co., Ltd., DH611) (before curing). Then, nitrogen was replaced at 50 ° C. for 30 minutes using an inert oven (manufactured by Yamato Scientific Co., Ltd., DN610I), the temperature was raised to 190 ° C. in about 15 minutes, and the mixture was dried at 190 ° C. for 30 minutes in a nitrogen atmosphere. A resin layer (absorption layer) was formed on the glass substrate (after curing). The thickness of the resin layer formed on the glass substrate was 2 μm. An optical filter was produced by forming a resin layer on the glass substrate in this way. The thickness of the resin layer was determined by measuring the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone with a micrometer, and determining the difference between the two.

(6) Measurement of transmission (absorption) spectrum of ethylene compound and optical filter (6-1) Measurement of absorption spectrum of ethylene compound Using a spectrophotometer (UV-1800, manufactured by Shimadzu Corporation), each ethylene compound in toluene The absorption spectrum was measured at a measurement pitch of 1 nm, and the light transmittance at a wavelength of 300 nm to 1100 nm was determined. The maximum wavelength λmax of the maximum absorption peak in the wavelength range of 300 nm to 800 nm was determined, and the results are summarized in Table 3. The absorption spectra of ethylene compound 1 and comparative ethylene compound 1 in toluene are shown in FIG.

(6-2) Measurement of transmission spectrum of optical filter For each optical filter having a resin layer formed on a glass substrate, the transmission spectrum was measured at a measurement pitch of 1 nm using a spectrophotometer (UV-1800, manufactured by Shimadzu Corporation). , The transmittance of light at a wavelength of 300 nm to 800 nm was determined. The transmission spectra of the optical filters before and after curing the resin layer were measured. The results are shown in FIGS. 2 to 12.

(6-3) Results As shown in FIG. 1, the absorption spectra of ethylene compound 1 and comparative ethylene compound 1 in toluene showed the maximum absorption peak at a wavelength of about 380 nm. As shown in FIGS. 2, 3, 7, 10, and 12, the transmission spectrum of the optical filter formed from the resin composition containing the ethylene compound or the squarylium compound does not change significantly before and after curing at 190 ° C. I couldn't see it. On the other hand, the transmission spectra of the optical filter formed from the resin composition containing the comparative ethylene compound and the squarylium compound are ultraviolet rays after curing at 190 ° C. as shown in FIGS. 4 to 6, 8, 9, and 11. ~ The transmittance in the purple area has increased. From these results, it can be seen that the ethylene compound of the present invention has excellent heat resistance.

(7) Adhesion evaluation (7-1) Initial peeling resistance test Cut the resin layer of the optical filter obtained above with a cutter (manufactured by NT, A-300), and make cuts in columns and rows at 2 mm intervals. By providing 10 cross-cut lines, ^{81 squares of 4 mm 2} were prepared to prepare a sample substrate for evaluation. This sample substrate was attached with a tape (3M (3M), Scotch (registered trademark) transparent adhesive tape, transparent beauty color (registered trademark)) to prevent air from entering, and left for 5 seconds. Then, the tape was peeled off from the sample substrate within 1 second, and evaluated according to the following criteria. The tape was peeled off so that the peeling force was constant in all the cells.
A: No peeling occurred in any of the 81 squares prepared. B: Peeling occurred in 1 to 9 squares of the 81 squares prepared. C: Of the 81 squares prepared. , 10 to 81 squares were peeled off

(7-2) Peeling resistance test after boiling in water The resin layer of the optical filter obtained above is cut with a cutter (A-300, manufactured by NT), and 10 cloths are made in columns and rows at 2 mm intervals. By providing a cut line, ^{81 squares of 4 mm 2} were prepared to prepare a sample substrate for evaluation. Next, this sample substrate was placed in ultrapure water heated to a boiling state and boiled for 2 hours. Subsequently, at room temperature, a tape (3M (3M), Scotch (registered trademark) transparent adhesive tape, transparent beauty color (registered trademark)) was attached to prevent air from entering, and the mixture was left for 5 seconds. Then, the tape was peeled off from the sample substrate within 1 second, and evaluated according to the following criteria. The tape was peeled off so that the peeling force was constant in all the cells.
A: No peeling occurred in any of the 81 squares prepared. B: Peeling occurred in 1 to 9 squares of the 81 squares prepared. C: Of the 81 squares prepared. , 10 to 81 squares were peeled off

(7-3) Results Table 4 shows the results of the initial peel resistance test and the peel resistance test after boiling of the optical filter prepared by using the polyarylate resin compositions 1, 3 to 8. As is clear from the results in Table 4, the optical filter formed from the resin composition containing the ethylene compound of the present invention and the silane coupling agent or a hydrolyzed product thereof has adhesion between the resin layer and the glass substrate. It became excellent.

The ethylene compound of the present invention can be used in an optical selective transmission filter or the like useful for applications such as optical devices, display devices, mechanical parts, electrical / electronic parts, etc. by blending it with a resin and molding it into a film or the like.

Claims (10)

An ethylene compound represented by the following formula (1).

[In formula (1), L, A alkylene group, - O-, - S -, - SO-, also methine group have A alkyl group (-C <),> C < 4 valent Represents a linking group of, or a linking group combining these
a represents an integer of 2 or more,
Each A independently represents a group represented by the following formula (2). ]

[In equation (2),
R ¹ represents a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group or a halogenoalkyl group.
R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group.
When ^{both R 1} and R ² are acyl groups, carboxylic acid ester groups or amide groups, R ¹ and R ² may be linked to each other to form a ring.
R ³ represents a hydrogen atom or an alkyl group
R ⁴ represents a hydrogen atom, an organic group or a polar functional group, and a plurality of R ^4s may be the same or different from each other.
X represents a sulfur atom
* Represents the binding site with the linking group L of the formula (1). ] The ethylene compound according to claim 1, wherein R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group or an amide group. The ethylene compound according to claim 1 or 2, which has a maximum absorption peak at a wavelength of 420 nm or less in an absorption spectrum in the wavelength range of 300 nm to 600 nm measured in toluene. An ultraviolet absorber containing the ethylene compound according to any one of claims 1 to 3. A resin composition containing the ethylene compound according to any one of claims 1 to 3 and a resin component. The resin composition according to claim 5, further containing a near-infrared absorbing dye and / or a visible light absorbing dye. The resin composition according to claim 5 or 6, further comprising at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolyzed condensate thereof. A cured product obtained by curing the resin composition according to any one of claims 5 to 7. An optical filter comprising the resin composition according to any one of claims 5 to 7 or the cured product according to claim 8. A sensor comprising the optical filter according to claim 9.

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