KR102253364B1 - Ethylene compound, ultraviolet absorber and resin composition - Google Patents

Abstract

상기 식에서, L은 2가 이상의 연결기를 나타내고, a는 2 이상의 정수를 나타내고, A는 각각 독립하여 하기 식(2)의기를 나타낸고,

상기 식에서, R¹은 시아노기, 아실기, 카복실기, 카복실산 에스테르기, 아미드기 또는 할로게노알킬기를 나타내고, R²는 수소 원자, 시아노기, 아실기, 카복실기, 카복실산 에스테르기, 아미드기, 탄화 수소기 또는 헤테로아릴기를 나타내고, R¹과 R²는 서로 연결해서 환을 형성하고 있을 수도 있고, R³은 수소 원자 또는 알킬기를 나타내고, R⁴는 수소 원자, 유기기 또는 극성 작용기를 나타내고, X는 황원자 또는 산소원자를 나타내고, *는 식(1)의 연결기(L)과의 결합부위를 나타낸다. Ethylene compound of the following formula (1), and a resin composition containing the same:

In the above formula, L represents a divalent or higher linking group, a represents an integer greater than or equal to 2, and A represents each independently a group represented by the following formula (2),

In the above formula, 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, a carboxylic acid ester group, an amide group, Represents a hydrocarbon group or a heteroaryl group, R ¹ and R ² may be connected 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, X represents a sulfur atom or an oxygen atom, and * represents the bonding site with the linking group (L) of formula (1).

Description

Ethylene compound, ultraviolet absorber and resin composition

The present invention relates to an ethylene compound capable of absorbing light in the ultraviolet to purple region, a resin composition containing the same, 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 have been known. As such a compound, for example, Patent Document 1 discloses a benzophenone compound, Patent Document 2 discloses a merocyanine compound, and Patent Document 3 discloses a triazine compound. In addition, Patent Documents 4 and 5 disclose a resin composition containing a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, or a benzophenone-based ultraviolet absorber, and an optical film formed from the resin composition.

Japanese Laid-Open Patent Publication H07-285927 Japanese Patent Laid-Open 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 molded into various shapes depending on the application and used. The use of resin molded articles is becoming more and more widened, and the use of such applications as heat resistance is required is also increasing. For example, in the case of 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, or mounting it on an electronic component by solder reflow, or by evaporating a dielectric multilayer film. In some cases, the UV absorber is required to have sufficient heat resistance so that the desired ultraviolet absorbing performance is exhibited even after passing through these processes when an ultraviolet absorber is included in the resin composition.

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

The present invention includes the following inventions.

[1] An ethylene compound characterized by the following formula (1):

In the above formula, L represents a divalent or more linking group, a represents an integer of 2 or more, and A each independently represents a group of the following formula (2),

In the above formula,

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 R ¹ and R ² together are an acyl group, a carboxylic acid ester group or an amide group, 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 ⁴ may be the same or different from each other,

X represents a sulfur atom or an oxygen atom,

* Indicates the bonding site with the connector (L) of 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] above, having a maximum absorption peak at a wavelength of 420 nm or less in an absorption spectrum in the range of 300 nm to 600 nm measured in toluene.

[4] An ultraviolet absorber comprising the ethylene compound according to any one of [1] to [3].

[5] A resin composition comprising the ethylene compound according to any one of [1] to [3] and a resin component.

[6] The resin composition according to [5], further comprising a near-infrared absorbing dye and/or a visible light absorbing dye in the above [5].

[7] The resin composition according to [5] or [6], further containing at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolyzate 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 described in [8].

[10] A sensor comprising the optical filter according to [9].

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

1 shows absorption spectra of the ethylene compound (1) obtained in Examples and the comparative ethylene compound (1) in toluene.
Fig. 2 shows a transmission spectrum of an optical filter formed of an epoxy resin composition (1) containing an ethylene compound (2) and a near-infrared absorbing dye obtained in Examples.
3 shows a transmission spectrum of an optical filter formed of an epoxy resin composition (2) containing an ethylene compound (14) obtained in Examples.
4 shows a transmission spectrum of an optical filter formed of an epoxy resin composition (3) containing a comparative ethylene compound (1) obtained in Examples and a near-infrared absorbing dye.
5 shows a transmission spectrum of an optical filter formed of an epoxy resin composition (4) containing a comparative ethylene compound (2) and a near-infrared absorbing dye obtained in Examples.
6 shows a transmission spectrum of an optical filter formed of an epoxy resin composition (5) containing a comparative ethylene compound (3) obtained in Examples and a near-infrared absorbing dye.
Fig. 7 shows a transmission spectrum of an optical filter formed of a cycloolefin resin composition (1) containing an ethylene compound (1) and a near-infrared absorbing dye obtained in Examples.
Fig. 8 shows a transmission spectrum of an optical filter formed of a comparative ethylene compound (1) obtained in Examples and a cycloolefin-based resin composition (2) containing a near-infrared absorbing dye.
9 shows the transmission spectrum of an optical filter formed of the comparative ethylene compound (3) obtained in Examples and the cycloolefin resin composition (3) containing a near-infrared absorbing dye.
10 shows a transmission spectrum of an optical filter formed of a polyarylate resin composition (1) containing an ethylene compound (12) and a near-infrared absorbing dye obtained in Examples.
Fig. 11 shows a transmission spectrum of an optical filter formed of a polyarylate resin composition (2) containing a comparative ethylene compound (1) and a near-infrared absorbing dye obtained in Examples.
12 shows the transmission spectrum of the optical filter formed of the polyarylate resin composition (4) containing the ethylene compound (14) and a near-infrared absorbing dye obtained in Examples.

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

In the above formula, L represents a divalent or more linking group, a represents an integer of 2 or more, and A each independently represents a group of the following formula (2),

In the above formula, 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, a carboxylic acid ester group, an amide group, Represents a hydrocarbon group or a heteroaryl group, and when R ¹ and R ² together are an acyl group, a carboxylic acid ester group or an amide group, R ¹ and R ² may be connected to each other to form a ring, and R ³ is a hydrogen atom or Represents an alkyl group, R ⁴ represents a hydrogen atom, an organic group or a polar functional group, a plurality of R ⁴ may be the same or different from each other, X represents a sulfur atom or an oxygen atom, * represents a linking group (L) of formula (1) It represents the bonding site of and.

In the group (A) of formula (2), ^{the ethylene structural moiety comprising R 1} and R ² functions as a chromophore. In formula (2), as R ¹ and R 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. In the above formula (2), R ¹ (or R ² ) may be a cis position or a trans position with respect to R ^3.

Examples ^{of the acyl group (alkanoyl group) of R 1} and R ² include metanoyl group, ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, and untecanoyl group. Diary, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group, and the like. In the acyl group, some of the hydrogen atoms 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 in the acyl group (the number of carbons excluding the substituent) is preferably 2 to 21, more preferably 2 to 11, and still more preferably 2 to 6.

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

Examples ^{of the alkyl group 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, octyl group, nonyl group , A linear or branched alkyl group such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group; Cyclic (alicyclic) alkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group, etc. are mentioned. In the alkyl group, some of the hydrogen atoms 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 (the number of carbons excluding the substituent) of the alkyl group is preferably 1 to 20, specifically, if it is a linear or branched alkyl group, the number of carbons is preferably 1 to 20, more preferably 1 to 10, further Preferably it is 1-5, and if it is a cyclic alkyl group, C4-10 are preferable and 5-8 are more preferable.

Examples ^{of the aryl group for R 11} include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and an indenyl group. In the aryl group, some of the hydrogen atoms 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 in the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, more preferably 6 to 12.

Examples of the aralkyl group for R ¹¹ include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a naphthylmethyl group. Some of the hydrogen atoms in the aryl group included in the aralkyl 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 aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, more preferably 7 to 15.

The amide group of R ¹ and R ² is the formula: *-C(=O)-NR ¹² R ¹³ , and * represents the bonding site of the ethylene double bond of the formula (2) to the carbon atom. In the above 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 R ¹² and R ¹³ an alkyl group, an acyl group and R ¹³ is an aryl group and an aralkyl group of the acyl groups described for the alkyl group of said R ^11, an aryl group, an aralkyl group, and R ¹ and R ² is referred to.

When R ¹ and R ² are both acyl ^{groups, R 1} and R ² may be linked to each other to form a ring, and in this case, ^{as a group formed by R 1} and R ² , the formula: *-C(=O) -R ¹⁴ -C(=O)-*. In the above formula, R ¹⁴ represents a linear or branched alkylene group, and * represents the bonding site of the ethylene double bond of formula (2) to a carbon atom. In the alkylene group, some of the hydrogen atoms 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 ^{number of carbon atoms in the alkylene group of R 14} (the number of carbon atoms excluding a substituent) is preferably 2 to 10, more preferably 3 to 8. Examples of the group (cyclic phase) formed by linking the acyl groups of R ¹ and R ^{2 to each other include a group represented by the following formula (3-1).}

When R ¹ and R ² are both a carboxylic acid ester group, R ¹ and R ² may be linked to each other to form a ring, and in this case, ^{as a group formed by R 1} and R ² , the formula: *-C(=O )-OR ¹⁵ -OC(=O)-*. In the above formula, R ¹⁵ represents a linear or branched alkylene group, and * represents the bonding site of the ethylene double bond of formula (2) to a carbon atom. In the alkylene group, some of the hydrogen atoms 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 ^{number of carbon atoms in the alkylene group of R 15} (the number of carbon atoms excluding a substituent) is preferably 1 to 8, more preferably 1 to 6. Examples of the group (cyclic phase) formed by linking the carboxylic acid ester groups of R ¹ and R ^{2 to each other include a group represented by the following formula (3-2).}

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

Examples of the halogenoalkyl group for R ¹ include those in which some or all of the hydrogen atoms of the alkyl group of ^{R 11 described above are substituted 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 for R 2} include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be either saturated or unsaturated, and may be linear, branched or cyclic. For specific examples of the aliphatic saturated hydrocarbon ^{group, reference is made to the description of the alkyl group of R 11} above, and for specific examples of the aliphatic unsaturated hydrocarbon group, a part of the carbon-carbon single bond of the alkyl group of R 11 described above is a double bond or a triple bond. What I changed to is mentioned. For specific examples of the aromatic hydrocarbon group (aryl group), reference is made to the description of the aryl group ^{of R 11.} The hydrocarbon group for R ² is preferably an aryl group.

Examples ^{of the heteroaryl group of R 2} include thienyl group, thiopyranyl group, isothiochromenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrrolidinyl group, pyrimidinyl group, pyridazinyl group, thia A sleepy group, an isothiazolyl group, a furanyl group, a pyranyl group, etc. are mentioned. In addition, the heteroaryl group preferably has a carbon atom bonded to the carbon atom of the ethylene double bond of formula (2), and more preferably the carbon atom adjacent to the hetero atom is bonded to the carbon atom of the ethylene double bond of formula (2). And, by this, the synthesis of the ethylene compound becomes easy. The number of carbon atoms in the heteroaryl group is preferably 3 to 18, more preferably 4 to 12.

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, whereby it becomes easy to effectively absorb light in the ultraviolet to purple region. ^{It is preferable that R 2} is not a hydrogen atom in cases where the absorption peak of the ethylene compound is desired to be set on the longer wavelength side, for example, in the case where light in the wavelength range of 350 nm to 420 nm is desired to be absorbed, for example, not in the complete ultraviolet region. Do.

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

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

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

For specific examples of the alkyl group of R ⁴ , reference is made to the description of the alkyl group ^{of R 11.} The alkyl group of R ⁴ may have a substituent, and examples of the substituents of the alkyl group include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group, a nitro group, an amino group, a sulfo group, and the like. I can.

An alkoxy group of R ^4, alkylthio group, alkoxycarbonyl group, specific examples of the alkyl group include groups alkylsulfonyl group, alkylsulfinyl is referred to the description of the alkyl groups of R ^4.

For specific examples of the aryl group and aralkyl group of R ⁴ , reference is made to the description of the aryl group and aralkyl group of R 11 described above. The aryl group contained in the aryl group or aralkyl group of R ⁴ may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, A thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

Aryloxy group of R ^4, arylthio, aryloxy carbonyl group, an aryl sulfonyl group, specific examples of the aryl groups include the aryl sulfinyl is referred to the description of the groups R ⁴ an aryl group.

For specific examples of the heteroaryl group of R ⁴ , reference is made to the description of the heteroaryl group ^{of R 2.} The heteroaryl group may have a substituent, and examples of 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, a nitro group, a thiocyanate group, an 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 the formula: -NR ²¹ R ²² , R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl 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, refer to the description above, and as the alkenyl group and the alkynyl group, a substituent in which a part of the carbon-carbon single bond of the alkyl group described above is replaced with a double bond or a triple bond These may be mentioned, and some of the hydrogen atoms may be substituted with halogen atoms in these substituents. Moreover, R ²¹ and R ²² may be connected to each other to form a ring.

Examples of the amide group for R ⁴ include formula: -NH-C(=O)-R ^23, wherein R ²³ is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. For specific examples of an alkyl group, an aryl group, an aralkyl group, and a heteroaryl group, the above description is referred to, and some of the hydrogen atoms may be substituted by halogen atoms.

Examples of the sulfonamide group of R ⁴ _{include formula: -NH-SO 2} -R ^24, wherein R ²⁴ is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. For specific examples of an alkyl group, an aryl group, an aralkyl group, and a heteroaryl group, the above description is referred to, and some of the hydrogen atoms may be substituted by halogen atoms.

Examples ^{of the halogeno group of R 4} include a fluoro group, a chloro group, a bromo group, and an iodine group.

R ⁴ is preferably at least one selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group and an aryl thi group. For example, when R ⁴ is a nitrogen-containing substituent, the substituent R ⁴ decomposes by heating or reaction, or changes to other structures, and the ethylene compound tends to exhibit coloration such as yellow, which is not very preferable. From the viewpoint of allowing 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 more preferably 1 to 3 carbon atoms. Do. ^{Among them, of the four R 4} bonded to the benzene ring of the group (A) of formula (2), 2 or more are preferably hydrogen atoms, more preferably 3 or more are hydrogen atoms, and all 4 are hydrogen atoms. It is particularly preferred.

X in the formula (2) represents a sulfur atom or an oxygen atom, whereby the ethylene compound becomes easy to stably absorb light in the ultraviolet to purple region. From the viewpoint of effectively absorbing light in the UV region, it is preferable that X is a sulfur atom.

In the group (A) of formula (2), X may be bonded to the ethylene structural part at the ortho position, may be missing at the meta position, or may be bonded at the para position. Moreover, it is preferable that X is bonded to a para position with respect to an ethylene structural part from a viewpoint of the ease of manufacture of an ethylene compound.

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

Examples of the linking group (L) include divalent linking groups such as an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, and -NH-; A trivalent linking group such as a methine group (-C<) and -N< which may have an alkyl group; Tetravalent linking groups such as >C<; And the linking group which combined these is mentioned. The alkylene group may be linear, branched or cyclic. Moreover, 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 bonding site of the group (A). Two groups (A) are bonded to the linking group (L) of formulas (4-1) to (4-9), and the linking group (L) of formulas (4-10) to (4-13) has three Group (A) is bonded, 4 groups (A) are bonded to the linking group (L) in formulas (4-14) to (4-15), and 5 groups (A) are in formula (4-16) Is bonded, and in Equation (4-17), six groups (A) are bonded.

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, an arylene group in which a part of the hydrogen atom may be replaced with a hydroxyl group and/or a thiol group, -O-, -S-, and a linking group in which these groups are combined are preferred (however, ether bonds and thioether bonds are not continuous). Further, the number of carbon atoms in the linear or branched alkylene group (continuous carbon number) is preferably 6 or less, more preferably 4 or less, and 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, further preferably 10 or less, and more preferably 8 or less. The number of carbon atoms in the arylene group is preferably 5 or more, more preferably 6 or more, further preferably 10 or less, and more preferably 8 or less.

As an ethylene compound, the ethylene compound of following formula (5) is especially preferable. Such an ethylene compound has, for example, a peak having an absorption maximum point in a wavelength range of 300 nm to 420 nm, can effectively absorb light in the ultraviolet to purple region, and is excellent in stability, and manufacture is facilitated. In the following formula (5), the description of ^{R 1a} and R ^1b refers to the description ^{of R 1 above, the description of R 2a} and R ^2b refers to the description of R ² above, and the description of R ^3a and R ^3b Reference is made to the description of R ^{3 above, and the description of X a} and X ^b is referred to above.

The ethylene compound of the present invention has a maximum absorption peak at a wavelength of 420 nm or less in an absorption spectrum of a wavelength 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. That is, when measuring the absorption spectrum in toluene, it is preferable that the ethylene compound has a peak having an absorption maximum point in the range of 300 nm to 420 nm, and the absorption maximum point of the absorption peak takes the maximum value in the range of 300 nm to 600 nm. Do. If the ethylene compound exhibits such an absorption spectrum, it can effectively absorb light in the ultraviolet to purple region. The maximum wavelength of the absorption peak is more preferably 310 nm or more, more preferably 315 nm or more, further preferably 410 nm or less, and even more preferably 400 nm or less.

When the absorbance of the ethylene compound at the maximum wavelength of the maximum absorption peak is 1, the peak width at the absorbance of 0.5 of the absorption peak is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less. When the ethylene compound exhibits such an absorption spectrum, it becomes one capable of selectively absorbing light in the ultraviolet to purple 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.

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

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

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 dissolving or dispersing in an arbitrary solvent (for example, water or an organic solvent). Therefore, the ultraviolet absorber may contain a solvent.

The number of ethylene compounds contained in the ultraviolet absorber may be one or two or more. UV absorbers other than the ethylene compound of the present invention, known UV absorbers (e.g., benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxadione compounds, cyanoacrylate compounds, benzoxazole compounds, Merocyanine-based compounds, triazine-based compounds, etc.) may also be included.

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, and L have the same meaning as in the above formula (1), and their family registration form is also as described above. Y represents a halogen atom. In addition, in the following, the group R4 is omitted and shown, and an example in which a compound providing a divalent linking group is used as the linking group (L) is shown.

First, by reacting the compound of formula (6) providing the precursor of the group (A) with the compound of formula (7) providing the linking group (L), The compound of formula (8) in which the precursor is bonded is obtained. The compound of formula (6) is a halogenophenylketone compound or a halogenophenylaldehyde compound, and as for the compound of formula (6), only one type may be used, or two or more types may be used. The compound of formula (7) is a compound having a hydroxyl group and/or a thiol group. By reacting the compound of formula (6) with the compound of formula (7), X (sulfur atom or oxygen atom) of the compound of formula (7) is nucleophilic to the carbon atom to which the halogen atom of the compound of formula (6) is bonded. And the compound of formula (8) in which the precursor of the group (A) is bonded to the linking group (L) is obtained.

As compound (7), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-ethane dithiol, 1,2-propane dithiol, 2-mercaptoethanol, thiodiglycol, bis(2-mer) Divalent linking groups (L) such as captoethyl) ether, bis(2-mercaptoethyl)sulfide, 1,3-bis(2-mercaptoethylthio)propane, cyclohexanediol, benzenediol, and bisphenol A Compounds to provide; Glycerol, dimercaprol, cyclohexanetriol, benzenetriol, trimethylolpropane trimercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) Compounds providing a trivalent linking group (L) such as -ethyl]-isocyanurate; Compounds providing a tetravalent linking group (L) such as erythritol, pentaerythritol tetrakismercaptoacetate, and pentaerythritol tetrakis (3-mercaptopropionate); Compounds that provide a pentavalent linking group (L) electrode such as ribitol; Compounds that provide a hexavalent linking group (L), such as dipentaerythritol hexamercaptoacetate and dipentaerythritol hexamercaptoacetate (3-mercaptopropionate), can be used.

Subsequently, the ethylene compound of the present invention of formula (10) is obtained by subjecting the compound of formula (8) and the compound of formula (9) to Knoevenagel condensation reaction. In the compound of formula (9), when the ^{methylene group between R 1} and R ² is interposed in a cyano group and/or a carbonyl group, the reactivity with the carbonyl group of the compound of formula (8) becomes particularly high. As for the compound of formula (9), only 1 type may be used and 2 or more types may be used.

As compound (9), acetonitrile, propionitrile, malononitrile, phenyl acetic acid ester, cyanoacetic acid ester, malonic acid diester, 2-cyano-N,N-dimethylacetamide, N-methylacetoacetamide , Acetoacetanilide, N,N,N',N'-tetramethyl malonamide, 1,3-cyclohexanedione, dimedone, meldrum acid, barbituric acid, and the like can be used.

It is preferable to carry out the above reaction in the presence of a solvent. Examples of the solvent usable include chlorine hydrocarbons such as chloroform and methylene chloride; Aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; Chlorine aromatics such as chlorotoluene and dichlorobenzene; Ethers such as tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, diisopropyl ether, and diethyl ether; Nitriles such as acetonitrile, propionitrile, acrylonitrile and butyronitrile; Alcohols such as methanol, ethanol, propanol, and butanol; Organic acids such as formic acid, acetic acid and propionic acid; And the like. These solvents may be used alone or in combination of two or more.

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

If necessary, the obtained ethylene compound can be suitably purified by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation, recrystallization, and crystallization.

The ethylene compound of the present invention can be mixed with a resin component to obtain a resin composition. Since the ethylene compound of the present invention is excellent in heat resistance, for example, even when it is blended with a thermoplastic resin and heat-molded, the ultraviolet absorbing effect can be favorably exhibited. In addition, the resin composition containing the ethylene compound of the present invention can suppress deterioration due to light in the ultraviolet to violet region, and cure it to form a resin molded body such as a film, thereby cutting the light in the ultraviolet to violet region. It can be applied to optical filters and the like. In addition, even when exposed to ultraviolet light during storage of a resin composition or resin molded body or during manufacturing and processing of an optical filter (e.g., vapor deposition or mounting, etc.), components other than those contained in the resin component or resin composition from the ultraviolet light ( The near-infrared absorbing pigment etc. mentioned later) can be protected, and the deterioration of these components can be suppressed.

The resin composition contains at least the ethylene compound of the present invention and a resin component. The number of ethylene compounds contained in the resin composition may be one or two or more. The resin composition is another ultraviolet absorber (for example, a benzotriazole-based compound, a benzophenone-based compound, a salicylic acid-based compound, a benzoxadione-based compound, a cyanoacrylate-based compound, a benzoxazole-based compound, a merocyanine-based compound, Triazine-based compounds, etc.) may also be contained.

The content of the ethylene compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.1% by mass or more, based on 100% by mass of the solid content of the resin composition, from the viewpoint of expressing the desired performance. Do. In addition, from the viewpoint of enhancing the moldability and film formability of the resin composition, the content of the ethylene compound in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, in 100% by mass of the solid content of the resin composition, It is more preferably 15% by mass or less. When the resin composition contains other ultraviolet absorbers, it is preferable that the total content thereof is in the above range. Further, the content of the other ultraviolet absorber is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 30 parts by mass or less, based on 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.

As the resin component contained in the resin composition, a known resin can be used. As a resin component, transparency is high, and it is preferable that the ethylene compound of the present invention can be dissolved or dispersed. When the resin composition also contains a near-infrared absorbing dye or a visible light absorbing dye as described later, it is preferable that the resin component can also dissolve or disperse the dye. By selecting such a resin component, it is possible to achieve both high transmittance in the wavelength region to be transmitted and high absorption in the wavelength region to be blocked.

As the resin component, not only the polymerized resin but also the resin raw material (including the precursor of the resin, the raw material of the precursor, the monomer constituting the resin, etc.) are incorporated into the resin by polymerization or crosslinking reaction when molding the resin composition. It can also be used. In the present invention, either resin is also contained in the resin component. In the latter case, part or all of the structure of the ethylene compound may be decomposed by unreacted products, reactive terminal functional groups, ionic groups, catalysts, acid/basic groups, etc. present in the reaction solution obtained in the polymerization reaction. Therefore, when there is such a concern, it is preferable to form a resin composition by blending an ethylene compound with the resin in which polymerization has been completed.

As the resin component, it is preferable to use a resin having high transparency, and thereby the properties of the ethylene compound contained in the resin composition can be suitably utilized. As a resin component, for example, (meth)acrylic resin, (meth)acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyolefin resin (e.g., polyethylin resin, polypropylene resin), cyclo Olefin resin, melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (for example, nylon), aramid resin, polyimide resin, polyamideimide resin, alkyd resin, phenol resin, epoxy resin, Polyester resin (e.g., 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 (e.g., (meth)acrylic silicone resin, alkyl polysiloxane resin, silicone urethane resin, Silicone polyester resin, silicone acrylic resin, etc.), fluorine resin (e.g., fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluorine resin (PFA), fluorinated polyaryl ether ketone (FPEK)), Fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyethernitrile (FPEN), etc.), and the like. Among these, polyimide resins, polyamideimide resins, (meth)acrylic resins, cycloolefin resins, epoxy resins, polyester resins, polyarylate resins, polyamide resins, and polycarbonate resins from the viewpoint of excellent transparency and heat resistance. , A polysulfone resin, and a fluorinated aromatic polymer are preferred.

Polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain, for example, by condensation polymerization of tetracarboxylic dianhydride and diamine to obtain polyamic acid, which is then dehydrated and cyclized (imidized). It can be manufactured by. As the polyimide resin, it is preferable to use an aromatic polyimide in which an aromatic ring is connected by an imide bond. Polyimide resins such as MITSUBISHI GAS CHEMICAL COMPANY. NEOPRIM (registered trademark) of INC., Kapton (registered trademark) of DuPond, Aurum (registered trademark) of Mitsui Chemicals, Inc., MELDIN (registered trademark) of Saint-Gobain SA, TPS of Tory Plastics Precision Co., Ltd. (Registered trademark) TI 3000 series, etc. can be used.

Polyamideimide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. As the polyamideimide resin, for example, Torlon (registered trademark) of Solvay Speciality Polymers Italy SpA, VALOMAX (registered trademark) of TOYOBO, TPS (registered trademark) TI 5000 series of Tory Plastics Precision Co., Ltd. can be used, for example. have.

The (meth)acrylic resin is a polymer having a repeating unit derived from (meth)acrylic acid or a derivative thereof, for example, a resin having a repeating unit derived from a (meth)acrylic acid ester such as a poly(meth)acrylic acid ester resin is preferably used. Is used. It is also preferable that the (meth)acrylic resin has a ring structure in the main chain, and contains carbonyl groups such as a lactone ring structure, a glutaric anhydride structure, a glutalimide structure, a maleic anhydride structure, and a maleimide ring structure. Ring structure; And carbonyl group-free ring structures such as an oxetane ring structure, an azetidine ring structure, a tetrahydrofuran ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, and a piperidine ring structure. Further, the carbonyl group-containing ring structure also includes a structure containing a carbonyl group derivative group such as an imide group. The (meth)acrylic resin having a carbonyl group-containing ring structure is, for example, Japanese Laid-Open Patent Publication No. 2004-168882, Japanese Laid-Open Patent Publication No. 2008-179677, International Publication No. 2005/54311, and Japanese Laid-Open Patent Publication 2007-31537. What is described in the issue or the like can be used.

The cycloolefin resin is not particularly limited as long as it is a polymer obtained by using a cycloolefin as at least a part of the monomer component and polymerizing it, and having an alicyclic structure in a part of the main chain. Examples of cycloolefin resins include TOPAS (registered trademark) of Polyplastics Co., Ltd., APEL (registered trademark) of Mitsui Chemicals, Inc., ZEONEX (registered trademark) and ZEONOR (registered trademark) of Zeon Corporation. JSR's Aton (registered trademark), etc. can be used.

Epoxy resin is a resin that can be cured by crosslinking an epoxy compound (prepolymer) in the presence of a curing agent or a curing catalyst. Examples of the epoxy compound include an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, and a hydrogenated epoxy compound. For example, fluorene epoxy (OGSOL (registered trademark) PG) manufactured by Osaka Gas Chemicals Co., Ltd. -100), Mitsubishi Chemical Corporation's bisphenol A type epoxy compound (JER (registered trademark) 828EL) or hydrogenated bisphenol A type epoxy compound (JER (registered trademark) YX8000), and Daicel Corporation's alicyclic epoxy compound (EHPE (EHPE(registered trademark) YX8000)). Registered trademark) 3150) or a bifunctional alicyclic epoxy compound (CELOXIDE (registered trademark) 2021P) or 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 condensation polymerization of a polyhydric carboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. For example, the OKP series of Osaka Gas Chemicals Co., Ltd. TRN series of TEIJIN LIMITED, TEONEX (registered trademark), Rynite (registered trademark) of DuPond, NOVAPEX (registered trademark) of Mitsubishi Chemical Corporation., NOVADURAN (registered trademark) of Mitsubishi Engineering-Plastics Corporation., TORAY INDUSTRIES, INC. Lumirror (registered trademark), Toraycon (registered trademark), and ELITEL (registered trademark) of Unitika Ltd. can be used.

The polyarylate resin is a polymer obtained by condensation polymerization of a dihydric phenol compound and a dibasic acid (eg, aromatic dicarboxylic acid such as phthalic acid), and has a repeating unit including an aromatic ring and an ester bond in the repeating unit of the main chain. As the polyarylate resin, for example, VECTRAN (registered trademark) of KURARAY CO., LTD., U-POLYMER (registered trademark) or unifiNER (registered trademark) of Unitika Ltd. 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 condensation polymerization of diamine and dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in its main chain, and nylon, for example, may be used as the amide resin. The polyamide resin may have an aromatic skeleton, and an aramid resin is known as such a polyamide resin. Aramid resins are preferably used in that they have excellent heat resistance and strong mechanical strength. For example, TEIJIN LIMITED's TOWARON (registered trademark), CONEX (registered trademark), DuPond's KEVLAR (registered trademark), and NOMEX (registered trademark) Etc. can be used.

Polycarbonate resin is a polymer containing a carbonate group (-O-(C=O)-O-) in the repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) of TEIJIN LIMITED, Eupilon (registered trademark) of Mitsubishi Engineering-Plastics Corporation., NOVAREX (registered trademark), Zanter (registered trademark), and SD POLYCA (registered trademark) of Sumika Styron Polycarbonate Limited. Etc. can be used.

Polysulfone resin is a polymer having an aromatic ring, a repeating unit containing a sulfonyl group (-SO2-) and an oxygen atom. Polysulfone resin, for example, SUMIKAEXCEL (registered trademark) PES3600P or PES4100P of Sumitomo Chemicals Co., Ltd., UDEL (registered trademark) P-1700 of Solvay Specialty Polymers Italy S.p.A, etc. can be used.

The fluorinated aromatic polymer is a polymer having an aromatic ring having at least one fluorine atom and a repeating unit containing at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Among these, it is preferable that it is a polymer essentially containing a repeating unit containing an aromatic ring having at least one fluorine atom and an ether bond. As the fluorinated aromatic polymer, those described in Japanese Unexamined Patent Application Publication No. 2008-181121 can be used, for example.

It is preferable that the resin component has high transparency, and thereby it becomes easy to apply the resin composition suitably to an optical use. The resin component preferably has a total light transmittance of 75% or more at a thickness of 0.1 mm, more preferably 80% or more, and even 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 95% or less, for example. The total light transmittance is measured according to JIS K 7105.

The resin component preferably has a high glass transition temperature (Tg), whereby the heat resistance of the resin composition and various molded articles obtained therefrom can be improved. The glass transition temperature of the resin component is, for example, preferably 110°C or higher, more preferably 120°C or higher, and still 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 less, for example, from the viewpoint of securing the molding processability of the resin composition.

The resin composition may contain a near-infrared absorbing dye and/or a visible light absorbing dye. When 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, light transmission in the ultraviolet to purple region and the red to near infrared region is suppressed and light in the visible region is transmitted preferentially. It can be used as a resin composition for filters. When the resin composition contains the ethylene compound of the present invention and a visible light absorbing dye, it can be used as a resin composition for a colored filter or a blue light reduction filter.

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

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

The near-infrared absorbing colorant and the visible light absorbing colorant may be an organic pigment, an inorganic pigment, or an organic-inorganic complex pigment (for example, an organic compound coordinated with metal atoms or ions), and are not particularly limited. As a near-infrared absorbing dye and a visible light absorbing dye, for example, a squarilium-based dye, a chromium-based dye, and copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as a central metal ion. Cyclic tetrapyrrole pigments (porphyrins, crawlins, phthalocyanines, naphthalocyanines, choline, etc.), cyanine pigments, azo pigments, quinone pigments, xanthene pigments, indoline pigments, arylmethane A dye, a quaterylene dye, a dimonium dye, a perylene dye, a quinacridone dye, an oxazine dye, a dipyrromethene dye, a nickel complex dye, and a copper ion dye. These pigments may be used alone or in combination of two or more. Among them, at least one selected from cyanine dyes, squarilium compounds, chromonium compounds, dipyrromethene dyes, and phthalocyanine compounds as near-infrared absorbing dyes and visible light absorbing dyes in that they can effectively absorb the desired wavelength light. It is preferable to use. As the near-infrared absorbing dye, it is preferable to use at least one selected from a squarilium compound, a chromonium compound, and a phthalocyanine compound from the viewpoint that it is easy to effectively absorb the light in the near-infrared region and increase the visible light transmittance.

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 0.01% by mass in 100% by mass of the solid content of the resin composition in terms of expressing the desired performance. It is preferable that it is more than that, 0.03 mass% or more is more preferable, and 0.1 mass% or more is still more preferable. In addition, from the viewpoint of enhancing the moldability and film formability of the resin composition, the content of the near-infrared absorbing dye and the visible light absorbing dye in the resin composition is preferably 25% by mass or less in 100% by mass of the solid content of the resin composition, and 20% by mass. The following is more preferable, and 15 mass% or less is still more preferable. In addition, the total content of the ethylene compound, the near-infrared absorbing dye and the visible light absorbing dye (or the total content of another ultraviolet absorber) is preferably 30% by mass or less, based on 100% by mass of the solid content of the resin composition, and 25% by mass. The following is more preferable, and 20 mass% or less is still more preferable.

In the case of using the resin composition as a resin composition for a light selective transmission filter that preferentially transmits light in the visible light region, as a near-infrared absorbing dye, for example, a squarylium compound of the following formula (11) or the following formula (12). It is preferred to use a chromonium compound. In the following formulas (11) and (12), R ²¹ to ^{R 24} each independently represent a group represented by the following formula (13) or formula (14).

In the above formula (13), ring P represents an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a condensed ring including a ring structure thereof, and R ³¹ to ^{R 33} are each independently a hydrogen atom, Represents an organic group or a polar functional group, and R ³² and R ³³ may be connected to each other to form a ring. In the above formula (14), R ³⁴ to ^{R 38} each 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 , R ³⁷ and R ^{Each of 38} may be connected to each other to form a ring. * Represents a bonding site with a 4-membered ring in formula (11) or a 5-membered ring in formula (12).

For details of the organic group and the polar functional group of ^{R 31} to ^{R 38} , reference is made to the description of the organic group and the polar functional group ^{of R 4.} When R ³¹ to ^{R 38} are independent ^{groups, it is preferable that R 31} to ^{R 38} are each independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amide group, or a hydroxy group. For details of these groups, reference is made to the above description ^{of R 4.}

Each ring structure formed by R ³² to ^{R 38} includes a hydrocarbon ring or a heterocycle, and these ring structures may or may not have aromaticity, but a non-aromatic hydrocarbon ring or a non-aromatic group It is preferable to be a summoning. Examples of the non-aromatic hydrocarbon ring include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; Cycloalkenes, such as cyclopentene, cyclohexene, cyclohexidiene (for example, 1,3-cyclohexidiene), cycloheptene, and cycloheptadiene, etc. are mentioned. As the non-aromatic heterocycle, at least one atom selected from N (nitrogen atom), S (sulfur atom) and O (oxygen atom) in which at least one carbon atom constituting the ring of the hydrocarbon ring as described above is used. There is a missing ring. Examples of the non-aromatic heterocycle include pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, piperidine ring, tetrahydropyran ring, tetrahydrothiopyran ring, morpholine ring, hexamethyleneimine ring, and hexamethylene oxide. A ring, a hexamethylene sulfide ring, a heptamethylene imine ring, etc. are mentioned.

In the group of formula (13), ^{the ring structure formed by linking R 32} and R ³³ is preferably a 4 to 9 membered unsaturated hydrocarbon ring, and among them, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc. Cycloalkanmonoene is more preferred. If the group of 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 is sharp.

Examples of the aromatic hydrocarbon ring of ring P of formula (13) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, a cyclotetra decapentaene 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, a furan ring, A thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a purine ring, a pteridine ring, and the like. The aromatic heterocycle may have only one ring structure, or may be a condensation of two or more ring structures. The condensed ring including these ring structures of ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are condensed, for example, an indole ring, an isoindole ring, a benzoimidazole ring, a quinoline ring, and a benzopyran ring. , An acridine ring, a xanthene ring, and a carbazole ring. By appropriately setting the ?-conjugated system of ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

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

For details of the squarilium compound and chromonium compound having the group of formula (13), the description of Japanese Unexamined Patent Application Publication No. 2016-74649 is referred to.

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

Or a group R ³⁶ in the formula (14) is an amino group, to amino groups of R ³⁶ and R ³⁵ are connected or form a ring, preferably forming a ring by connecting with more R ³⁷ excessively. In this case, the wavelength of the maximum absorption point shifts to the long wavelength side (for example, 685 nm or more) to increase the light transmittance in the red region, so that the color sense of transmitted light can be brought close to the actual one.

In the squarilium compound and the chromonium compound having a group of formula (14), the benzene rings on both sides of the squarylium skeleton or the chromonium skeleton may be connected by a linking group. As such a compound, for example, a squarilium compound disclosed in Japanese Unexamined Patent Application Publication No. 2015-176046 can be found.

The resin composition is at least one selected from 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 the support (hereinafter, these are summarized together. It is preferable to contain (sometimes called a "specific silane compound"). As the silane coupling agent used herein, a silane coupling agent containing an epoxy group, an amino group, or a mercapto group is preferable, and among them, an epoxy group-containing silane coupling agent is preferable. When such a silane coupling agent is used, while the ethylene compound is contained in the resin composition, the adhesion of the resin layer to the support can be improved.

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 or more epoxy groups, and may contain only one or more alkoxysilyl groups.

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 the above formula, 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 to 3, m represents an integer of 0 to 2, and n represents an integer of 1 to 3 Represents an integer. When k is 2 or more, a plurality of R ^41s may be the same or different from each other, and when m is 2, a plurality of R ^42s may be the same or different from each other, and when n is 2 or more, a plurality of ORs ⁴³ May be the same or different from each other. R ⁴¹ and R ⁴² and OR ⁴³ and OH are groups directly bonded to Si, respectively.

In the above formula (15), ^{the epoxy group-containing group of R 41} is not particularly limited as long as it contains an epoxy group, and a glycidoxy group-containing group and a cycloalkene oxide (alicyclic epoxy group)-containing group can be mentioned. The glycidoxy group and cycloalkene oxide may be bonded to the silicon atom through a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). It is preferable that only one epoxy group is contained in R41. Examples of the epoxy group-containing group of R41 include glycidoxy group, 3-glycidoxypropyl group, 8-(glycidoxy)-n-octyl group, 3,4-epoxycyclohexyl group, 2-(3,4-epoxycyclohexyl group ) Ethyl group, etc. are mentioned. In addition, 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 away from the silicon atom. For example, the glycidoxy group or cycloalkene oxide is directly bonded to the silicon atom. Or bonded to a silicon atom through an alkylene group having 1 to 6 carbon atoms.

In the above formula (15), ^{the alkyl group of R 42} and R ⁴³ preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and still more preferably 1 to 3. As R ⁴² , a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferably mentioned. As OR ^{43, a} methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are preferably mentioned.

In the above formula (15), k is preferably 1 or 2, more preferably 1, whereby it becomes easy to increase the adhesion of the support body number of the resin layer. Moreover, 0 or 1 is preferable, as for m, 0 is more preferable, and 2 or 3 is preferable for n.

When the epoxy group-containing silane coupling agent contains a plurality of alkoxysilyl groups, a polymer type polyfunctional epoxy group-containing silane coupling agent (hereinafter, simply referred to as a ``polymer type silane coupling agent'' may be used) as the silane coupling agent. I can. The polymeric 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 may contain a plurality of alkoxysilyl groups in one molecule and a plurality of epoxy groups. In addition, polysiloxane is not contained in the organic chain of the polymeric silane coupling agent. Since the polymeric silane coupling agent can have a plurality of alkoxysilyl groups and epoxy groups in one molecule in this way, a large number of reaction points with the resin or the support are formed, and the adhesion of the resin layer to the support can be improved.

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. In addition, the hydrolyzed condensate of the epoxy group-containing silane coupling agent can be obtained by dehydrating and condensing silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). Usually, when the silane coupling agent is hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and at the same time, the dehydration and condensation reaction of the silanol group contained in the hydrolyzate also occurs, so that the hydrolyzed condensate of the silane coupling agent is also easily obtained. The hydrolyzed condensate of the silane coupling agent may be a hydrolyzate dehydration condensate of the same type of a silane coupling agent, or a hydrolyzate dehydration condensate of a heterogeneous 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, the alkoxysilane of formula (15)), and more preferably, an alkoxysilane having an epoxy group (For example, the hydrolyzed condensate of the alkoxysilane of the said formula (15)) is contained. As the dehydration condensate in this case, for example, when the weight average molecular weight of the specific silane compound contained in the resin composition is measured, the molecular weight of the pentameric equivalent (however, all alkoxy groups are to be hydroxyl groups) is less than or equal to the molecular weight. It is preferable, and it is more preferable that it is less than or equal to the molecular weight of a tetramer. As a specific value of the weight average molecular weight, for example, 300 or more are preferable, 1000 or less are preferable, 800 or less are more preferable, and 600 or less are still more preferable. In addition, the total content ratio of the hydrolyzate and the hydrolyzed condensate of the epoxy group-containing silane coupling agent in the characteristic silane compound (1) 00% by mass is preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass or more. This 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, and 20% by mass or less in 100% by mass of the solid content of the resin composition. It is preferable, and 10 mass% or less is more preferable, and 5 mass% or less is still more preferable.

The content of the specific silane compound in the resin composition may be required by gas chromatography or high performance liquid chromatography. The specific silane compound contained in the resin composition is quantified for each type by gas chromatography or high performance liquid chromatography, and the content of the specific silane compound can be calculated from the total. When a dehydration condensate of a silane coupling agent (oligomer such as a dimer or a trimer) is contained, gel permeation chromatography analysis or the like can be combined to determine the presence form of the dehydrated condensate. For example, in the case of hydrolysis or dehydration condensation of an epoxy group-containing silane coupling agent, the hydrolyzate and the hydrolyzate of the hydrolyzate and the hydrolyzate are subtracted from the amount of the silane coupling agent used initially by subtracting the residual amount after hydrolysis or dehydration condensation. The content of the decomposition condensate can be calculated.

The resin composition may contain a solvent. For example, in the case where the resin composition is a coated resin composition, coating of the resin composition becomes easy by including a solvent. The coated resin composition can be obtained, for example, by dissolving an ethylene compound in a solvent containing a resin component or dispersing an ethylene compound in a solvent (dispersion medium) containing a resin component. The solvent may function as a solvent (solvent) for the ethylene compound, or may function 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 (ether compounds, ester compounds, ether ester compounds, etc.); Amides such as N,N-dimethylacetamide; Esters such as ethyl acetate, propyl acetate, and butyl acetate; Pyrrolidones such as N-methyl-pyrrolidone (specifically, 1-methyl-2-pyrrolidone, etc.); Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as cyclohexane and heptane; Ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether; Alcohols such as methanol, ethanol, propanol, and butanol; And the like. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 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 modifier, and thereby, when the resin composition is cured to form a resin layer, it is possible to suppress the occurrence of external defects such as striation and recesses in the resin layer. The type of the surface modifier is not particularly limited, and a siloxane-based surfactant, an acetylene glycol-based surfactant, a fluorine-based surfactant, an acrylic leveling agent, and the like can be used. As the surface modifier, for example, BYK (registered trademark) series of BYK Japan KK or KF series of Shin-Etsu Chemical Co., Ltd. can be used.

The resin composition may contain a dispersant, and thereby, the dispersibility of the ethylene compound in the resin composition can be stabilized and re-aggregation can be suppressed. The type of dispersant is not particularly limited, Efka Additives' EFKA series, BYK Japan KK's BYK (registered trademark) series, Japan The Lubrizol Corporation's Solsperse (registered trademark) series, Kusumoto Chemicals, Ltd.'s DISPARLON (registered trademark) Series, AJISPER (registered trademark) series of Ajinomoto Fine-Techno Co., Inc., KP series of Shin-Etsu Chemical Co., Ltd., Polyflow series of KYOEISHA CHEMICAL Co., LTD., MEGAFAC of D IC　 Corporation. Trademark) series, San Nopco Limited's disperade, etc. can be used.

The resin composition may contain various additives such as plasticizers, surfactants, viscosity modifiers, defoaming agents, preservatives, specific resistance modifiers, and adhesion improvers, as necessary.

It can be set as a cured product by curing a resin composition. The resin composition may be cured by a reaction of a resin component (for example, a polymerization reaction or a crosslinking reaction), or may be cured by drying or heat removal of the solvent contained in the resin composition. Examples of such resin compositions include thermoplastic resin compositions that can be molded by injection molding or extrusion molding, or spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, and screen printing. Painted resin compositions can be used so that they can be coated by a method, a flexo printing method, an inkjet method, a slit coating method, or the like. In addition, in the present invention, "cured" means a state in which the fluidity of the resin composition is lowered and substantially does not have fluidity. The "curing" includes a case where the resin composition becomes hard due to a reaction of the resin (for example, a polymerization reaction or a crosslinking reaction), or a case where the resin composition becomes hard due to the removal of the solvent contained in the resin composition.

When the resin composition is a thermoplastic resin composition, a cured product can be obtained by performing injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like of the resin composition. In this method, a thermoplastic resin is used as a resin component, an ethylene compound is blended with the thermoplastic resin, and heat-molded to obtain a molded article. For example, an ethylene compound may be added to the powder or pellet of the base resin, heated to about 150°C to 350°C, dissolved, and then molded. The shape of the molded product is not particularly limited, but plate shape, sheet shape, granular shape, powder shape, block shape, particle agglomerate shape, spherical shape, elliptical spherical shape, lens shape, cube shape, column shape, rod shape, cone shape, tube shape, needle shape , A fibrous shape, a hollow fiber shape, a porous shape, etc. are mentioned. In addition, when kneading the resin, an additive used in ordinary resin molding such as a plasticizer may be added.

When the resin composition is a coated resin composition, a liquid or paste resin composition containing an ethylene compound and a resin component is coated on a substrate (for example, a resin plate, a film, a glass plate, etc.) to a thickness of 200 μm. The following film form or sheet-like cured product having a thickness of more than 200 µm can be obtained. The cured product thus obtained may be peeled off from the substrate and treated as a film or sheet, or may be handled integrally with the substrate.

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 substrate, the cured product may be formed only on one side of the substrate, or may be formed on both sides. In addition, the integrated cured product and the substrate can be formed by thermocompressing or chemical bonding a molded article formed of a resin composition with the substrate.

Since the ethylene compound of the present invention is excellent in heat resistance, even when it is blended with a thermoplastic resin and heat-molded, or when it is integrated with a support by thermocompression or chemical bonding, the ultraviolet absorbing effect can be favorably exhibited. In addition, resins that require thermosetting reaction at high temperatures (for example, polyimide precursors, epoxy resins, acrylic resins, etc.) or resins that require drying at high temperatures (for example, resins or glass transitions containing a high boiling point solvent) Even in the case of molding using a resin having a high temperature), the ultraviolet absorption effect can be favorably exhibited due to the excellent heat resistance of the ethylene compound.

The ultraviolet absorber or resin composition containing the ethylene compound of the present invention or a cured product thereof is a container for containing coating glass, resin glass, building materials such as interior and exterior materials, paints, adhesives, automobile parts, food, pharmaceuticals, cosmetics, chemical agents, etc., 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.), telephone cable sheath material used in electric wires, UV light source Irradiation device member, fiber, display member, touch panel, optical filter member, optical sensor member, surface protection member such as cover glass or cover panel, filter member that removes harmful rays to the human body, various sensor members (malfunction) Prevention), lighting members, solar cell members, signboards, signs, and the like.

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

Imaging devices such as mobile phone cameras, digital cameras, automobile-mounted cameras, video cameras, and display devices (LEDs, etc.) are generally used for image pickup devices that convert light from a subject into electrical signals and output them. For example, a light-receiving element such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) or a lens is provided, and since it is high-performance, optical noise that interferes with image processing and the like (e.g., ghost or flare) is provided. A light selective transmission filter for removing) may be provided. Such a light selective transmission filter is usually provided with a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately stacked, and the dielectric multilayer film adjusts the thickness of each layer of the high refractive index material layer and the low refractive index material layer. , It is possible to block the incidence of light in the desired wavelength range.

However, in the dielectric multilayer film, since the cut-off wavelength range or the transmission wavelength range is changed by the incident angle, when the incidence angle changes from the vertical direction to the oblique direction, the cut-off wavelength range or the transmission wavelength range shifts to the short wavelength side. Therefore, in the dielectric multilayer film, it may not be possible to sufficiently block light in the desired wavelength range with respect to the transmitted light in the oblique direction, or the light in the visible light region may be blocked to change the color sense. In particular, in recent years, the image pickup device is required to be miniaturized and thinner. Accordingly, since the distance between the lens and the light-receiving device is shortened, there is a need for the light-receiving device to further receive the transmitted light from an oblique direction. In this case, since the dependence on the angle of incidence of the cut-off wavelength region and the transmission wavelength region becomes stronger, the shift of light in the short wavelength region, that is, light in the ultraviolet to violet region, which has had little effect in the prior art, to the short wavelength side becomes present.

The resin composition of the present invention contains the ethylene compound described above, and since this ethylene compound exhibits a sharp absorption peak in the ultraviolet to violet region, the optical filter formed of the resin composition selectively selects light in the ultraviolet to violet region. It can absorb and can reduce the dependence of the incident angle on the short wavelength side of the visible light region. In addition, when the resin composition contains the near-infrared absorbing dye as well as the ethylene compound, the optical filter formed of the resin composition can reduce the dependence of the incident angle on both the short wavelength side and the long wavelength side of the visible light region. In addition, since the ethylene compound contained in the optical filter is excellent in heat resistance, decomposition or volatilization of the ethylene compound is suppressed even when the resin composition is heat-molded or heat-cured, or when a dielectric multilayer film is provided by evaporation. -It becomes a thing that can effectively block light in a purple region. In addition, even when the optical filter is exposed to ultraviolet light during storage, manufacturing, and processing (for example, vapor deposition or mounting), deterioration of the resin component or near-infrared absorbing dye caused by the ultraviolet light can be suppressed.

The optical filter may be formed of a single or a plurality of resin layers, or may be formed integrally with a support. In the filter integrated with the support, for example, the resin composition is applied to the surface of the support (or the surface of the other layer in the case of having another layer such as a binder layer between the support and the resin layer) by a spin coating method or a solvent casting method. It can be formed by applying, drying or curing. Further, a filter can be formed by thermocompressing a planar molded body formed of a resin composition with respect to the support body.

The resin layer formed of the resin composition may be provided only on 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 securing the desired near-infrared ray blocking performance, for example, 0.5 µm or more is preferable, 1 µm or more is more preferable, 2 µm is more preferable, and 1 mm. The following are preferable, 500 micrometers or less are more preferable, and 200 micrometers or less are still more preferable. In the case of forming a resin layer by coating a resin composition coated on a support body or the like, since the strength of the filter can be secured by the support body, the thickness of the resin layer can be further reduced. When forming the resin layer 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. The resin plate or resin film used for the support is preferably formed of, for example, the resin component described above. From the viewpoint of enhancing the heat resistance of the optical filter, it is preferable to use a glass substrate as a support, and the thus formed optical filter can be mounted on an electronic component by, for example, solder reflow. In addition, even if the glass substrate is exposed to a high temperature, cracking or warping is unlikely to occur, so it becomes easy to secure adhesion to the resin layer. In the case of using a glass substrate as a support, a binder layer formed of, for example, a silane coupling agent may be formed between the support and the resin layer, whereby the adhesion between the resin layer and the glass substrate can be improved.

The thickness of the support (substrate) is, for example, preferably 0.05 mm or more from the viewpoint of securing strength, more preferably 0.1 mm or more, and 0.4 mm or less from the viewpoint of thinning, and more preferably 0.3 mm or less. Do.

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

The optical filter may have an anti-reflective or anti-glare layer (anti-reflective film) that reduces see-through of a fluorescent lamp, a layer having scratch-preventing properties, a transparent substrate having other functions, and the like. The optical filter may have an ultraviolet reflecting film or a near infrared reflecting film on the resin layer. It is preferable that the ultraviolet reflecting film or the near-infrared reflecting film is provided on the light incident side rather than the resin layer. If an ultraviolet reflective film or near-infrared reflective film is provided on the optical filter, it is possible to further block ultraviolet rays or near-infrared rays from transmitted light of the optical filter. The ultraviolet reflective film and the near-infrared reflective film may have an ultraviolet reflecting function and a near infrared reflecting function of Hannah.

The ultraviolet reflective film, near-infrared reflective film, and antireflection film (visible light antireflection film) can be constituted by a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately stacked. Therefore, in the case of imparting such a function to the optical filter, it is preferable that the optical filter has a dielectric multilayer film. As the 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 of generally 1.7 to 2.5 is 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; Nitrides such as silicon nitride; The oxides and mixtures of the nitrides, or those in which metals such as aluminum or copper or carbon are doped thereon (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), and the like are exemplified. 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 of generally 1.2 to 1.6 is selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

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 containing a small amount of tin oxide are dispersed.

It is preferable that the thickness of the optical filter is, for example, 1 mm or less. Thereby, for example, it is possible to sufficiently respond to the request for miniaturization of the imaging device. The thickness of the optical filter is more preferably 500 µm or less, still more preferably 300 µm or less, still more preferably 150 µm or less, further preferably 30 µm or more, and still more preferably 50 µm or more.

The optical filter can be used as one for sensor constituent members 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 light from a subject into an electrical signal and outputs it, and includes a Charge Coupled Device (CCD) or Complementary Metal-Oxide Semiconductor (CMOS). The image sensor can be used for mobile phone cameras, digital cameras, vehicle-mounted cameras, CCTV, display devices (LEDs, etc.). The sensor includes one or two or more of the above optical filters, and has another filter (eg, a visible light cut filter, an infrared cut filter, an ultraviolet cut filter, etc.) or a lens as necessary.

This application claims the benefit of priority based on Japanese Patent Application No. 2017-132977 filed on July 06, 2017. The entire contents of the specification of Japanese Patent Application No. 2017-132977 filed on July 06, 2017 are incorporated herein by reference.

Example

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, but is carried out by adding appropriate modifications within the range that may be suitable for the purpose of the preceding and following. It is also possible, but all of them are included in the technical scope of the present invention.

(1) Synthesis of compound

(1-1) Synthesis example 1: Synthesis of ethylene compound (1)

To a 200 mL 4nr-flask, 4.98 g (0.039 mol) of 4-fluorobenzaldehyde, 2.72 g (0.020 mol) of bis(2-mercaptoethyl) ether, 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile were added. Then, under nitrogen flow (10 ml/min), the mixture was reacted at 60° C. for 12 hours while stirring using a stirring blade. After completion of the reaction, after filtering out insoluble matters by filtration under reduced pressure, the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 ml 4-neck flask, and 5.19 g (0.079 mol) of malononitrile, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added thereto, followed by reaction for 4 hours under reflux conditions. Made it. After completion of the reaction, the solvent was distilled using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 6.2 g of ethylene compounds (1). The yield for 4-fluorobenzaldehyde was 71.3 mol%. About 5 mg of the obtained compound was aliquoted, diluted in a predetermined amount of a deuterated solvent (dichloroform or heavy dimethyl sulfoxide), and ^{measured by 1} H-NMR to determine the structure.

(1-2) Synthesis example 2: Synthesis of ethylene compound (2)

In Synthesis Example 1, 15.9 g of ethylene compounds (2) shown in Table 1 were obtained in the same manner as in Synthesis Example 1 except that methyl cyanoacetate was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 87.4 mol%.

(1-3) Synthesis example 3: Synthesis of ethylene compound (3)

In Synthesis Example 1, 3.4 g of ethylene compounds (3) shown in Table 1 were obtained in the same manner as in Synthesis Example 1 except that dimethyl malonate was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 35.7 mol%.

(1-4) Synthesis example 4: Synthesis of ethylene compound (4)

In Synthesis Example 3, 6.1 g of ethylene compounds (4) shown in Table 1 were obtained in the same manner as in Synthesis Example 3, except that piperidine and equivalent moles of acetic acid were added and used. The yield for 4-fluorobenzaldehyde was 80.0 mol%.

(1-5) Synthesis example 5: Synthesis of ethylene compound (5)

In Synthesis Example 1, 1.3 g of ethylene compounds (5) shown in Table 1 were obtained by the same procedure as in Synthesis Example 1 except that butyl cyanoacetate was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 14.8 mol%.

(1-6) Synthesis example 6: Synthesis of ethylene compound (6)

In Synthesis Example 1, 1.6 g of ethylene compounds (6) shown in Table 1 were obtained by the same procedure as in Synthesis Example 1 except that isobutyl cyanoacetate was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 18.1 mol%.

(1-7) Synthesis example 7: Synthesis of ethylene compound (7)

In Synthesis Example 1, 2.5 g of ethylene compounds (7) shown in Table 1 were obtained in the same manner as in Synthesis Example 1 except that 2-ethylhexyl cyanoacetic acid was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 24.2 mol%.

(1-8) Synthesis example 8: Synthesis of ethylene compound (8)

In Synthesis Example 1, 5.8 g of ethylene compounds (8) shown in Table 1 were obtained in the same manner as in Synthesis Example 1 except that meldrumic acid was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 49.1 mol%.

(1-9) Synthesis example 9: Synthesis of ethylene compound (9)

In Synthesis Example 1, 7.3 g of ethylene compounds (9) shown in Table 2 were obtained by the same procedure as in Synthesis Example 1, except that 1,3-dimethylbarbituric acid was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 58.9 mol%.

(1-10) Synthesis example 10: Synthesis of ethylene compound (10)

Ethylene compound (10) shown in Table 2 in the same procedure as in Synthesis Example 2, except that ethylene glycol bis (2-mercaptoethyl) ether was used instead of bis (2-mercaptoethyl) ether in Synthesis Example 2 3.8g was obtained. The yield for 4-fluorobenzaldehyde was 75.6 mol%.

(1-11) Synthesis example 11: Synthesis of ethylene compound (11)

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

(1-12) Synthesis example 12: Synthesis of ethylene compound (12)

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

(1-13) Synthesis example 13: Synthesis of ethylene compound (13)

In a 200 ml 4-neck flask, 4-chlorobenzaldehyde 4.61 g (0.0328 mol), ethylene glycol bis (2-mercaptoethyl) ether 2.92 g (0.016 mol), potassium carbonate 6.63 g (0.048 mol), tetrabutyl 0.52 g (0.0016 mol) of ammonium bromide and 30.11 g of acetonitrile were added, and the mixture was reacted at 75° C. for 6 hours while stirring using a stirring blade under nitrogen flow (10 ml/min). After the reaction was completed, insoluble matters were filtered off by filtration under reduced pressure, and then the solvent was distilled off using an evaporator. The obtained concentrate was put into a 200 ml flask for 4 servings, and 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, followed by reaction under reflux conditions for 2 hours. After completion of the reaction, the solvent was distilled using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 7.0 g of ethylene compounds (13) shown in Table 2. The yield for 4-chlorobenzaldehyde was 92.0 mol%. About 5 mg of the obtained compound was aliquoted, diluted in a predetermined amount of a deuterated solvent (dichloroform or didimethyl sulfoxide), and the structure was determined by ^{1 H-NMR measurement.}

(1-14) Synthesis example 14: Synthesis of ethylene compound (14)

To a 200 mL 4-neck flask, 4.75 g (0.010 mol) of the ethylene compound (13) obtained in Synthesis Example 13, 0.19 g (0.001 mol) of p-toluenesulfonic acid monohydrate, and 80 g of 1-butanol were added, The reaction was carried out for 5 hours under reflux conditions while stirring using a stirring blade under nitrogen flow (10 mL/min). After completion of the reaction, the solvent was distilled using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 4.9 g of ethylene compounds (14) shown in Table 2. The yield for 4-chlorobenzaldehyde was 83.5 mol%. About 5 mg of the obtained compound was aliquoted, diluted in a predetermined amount of a deuterated solvent (dichloroform or didimethyl sulfoxide), and the structure was determined by ^{1 H-NMR measurement.}

(1-15) Synthesis example 15: Comparison Synthesis of Ethylene Compound (1)

To a 200 mL 4-neck flask, 4-fluorobenzaldehyde 3.85 g (0.031 mol), 4-chlorobenzyl mercaptan 5.02 g (0.031 mol), potassium carbonate 8.57 g (0.062 mol), and acetonitrile 36 g were added, Under nitrogen flow (10 ml/min), the mixture was reacted at 60° C. for 12 hours while stirring using a stirring blade. After completion of the reaction, after filtering out insoluble matters by filtration under reduced pressure, the solvent was distilled off using an evaporator. The obtained concentrate was put in a 200 ml 4-neck flask, and 4.10 g (0.062 mol) of malononitrile, 2.64 g (0.031 mol) of piperidine, and 41 g of methanol were added thereto, followed by reaction for 4 hours under reflux conditions. Made it. After completion of the reaction, the solvent was distilled using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 8.9 g of a comparative ethylene compound (1) shown in Table 2. The yield for 4-fluorobenzaldehyde was 92.6 mol%.

(1-16) Synthesis example 16: Synthesis of comparative ethylene compound (2)

In Synthesis Example 15, 1.7 g of comparative ethylene compounds (2) shown in Table 2 were obtained by the same procedure as in Synthesis Example 15 except that methyl cyanoacetate was used instead of malononitrile. The yield for 4-fluorobenzaldehyde was 29.9 mol%.

(1-17) Synthesis example 17: Synthesis of comparative ethylene compound (3)

In Synthesis Example 15, 3.5 g of comparative ethylene compounds (3) shown in Table 2 were obtained in the same manner as in Synthesis Example 15 except that 4-isopropylbenzenethiol was used instead of 4-chlorobenzyl mercaptan. The yield for 4-fluorobenzaldehyde was 71.9 mol%.

(2) Epoxy resin ( EP Resin) Preparation of the composition

(2-1) Preparation of curing catalyst

According to the synthesis method described in International Publication No. 1997/031924, 255 g of an ISOPAR (registered trademark) E solution of ANDOH PARACHEMIC CO., LTD. having a TPB (tris (pentafluorophenyl) borane) content of 7% was prepared. Water was added dropwise to this solution at 60° C. to precipitate white crystals, cooled to room temperature, filtered with suction, and washed with n-heptane. The obtained cake was dried under reduced pressure at 60° C., and 18.7 g of white crystals of TPB/hydrate (TPB-containing powder) were obtained. This complex had a water content of 9.2% (Carl Fisher water system) and a TPB content of 90.8%. The dried complex was subjected to ¹⁹ F-NMR analysis and GC analysis, but no peaks other than TPB were detected. 2.0 g of the obtained TPB/hydrate complex and 1.1 g of toluene were blended, and mixed at room temperature for 10 minutes. After that, 2.6 g of a 2 mol/L ammonia/ethanol solution was added, followed by mixing at room temperature for 60 minutes to obtain a homogeneous solution of the TPB catalyst. This was used as a cation hardening catalyst.

(2-2) Silane Hydrolyzate Preparation of solution

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

(2-3) Preparation of epoxy resin composition (1)

As an epoxy resin, 100 parts by mass of a 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct (Daicel Corporation., EHPE3150) was added to 2,2-bis(hydroxymethyl)-1-butanol, and a solvent. As 150 parts by mass of toluene and 75 parts by mass of o-xylene, 8.9 parts by mass of the squarilium compound (A) shown below as a near-infrared absorbing dye (described in Example 1-18 of Japanese Laid-Open Patent Publication No. 2016-74649), Synthesis Example 8.4 parts by mass of the ethylene compound (2) obtained in 2, and 0.3 parts by mass of BYK Japan KK's BYK-306 (polyether-modified polydimethylsiloxane) as a surface modifier were blended, and uniformly mixed at 40°C. After cooling the obtained mixture to 25°C, 2.5 parts by mass of the cation curing catalyst obtained above and 10 parts by mass of a silane hydrolyzate solution were added and uniformly mixed, and this was mixed with a filter having a pore diameter of 0.45 µm (GL Sciences Inc., ratio). It filtered with aqueous 13N) to remove a foreign substance, and obtained the epoxy resin composition (1).

(2-4) Preparation of epoxy resin composition (2)

In the preparation example of the above epoxy resin composition (1), the epoxy resin composition (2) was carried out in the same procedure except that the near-infrared absorbing dye was not used and the ethylene compound (14) was used in place of the ethylene compound (2). ).

(2-5) Preparation of epoxy resin composition (3)

In the preparation example of the above-mentioned epoxy resin composition (1), the epoxy resin composition (3) was obtained by the same procedure except that the comparative ethylene compound (1) was used instead of the ethylene compound (2).

(2-6) Preparation of epoxy resin composition (4)

In the preparation example of the above-mentioned epoxy resin composition (1), an epoxy resin composition (4) was obtained by the same procedure except that the comparative ethylene compound (2) was used instead of the ethylene compound (2).

(2-7) Preparation of epoxy resin composition (5)

In the preparation example of the above-mentioned epoxy resin composition (1), the epoxy resin composition (5) was obtained by the same procedure except that the comparative ethylene compound (3) was used instead of the ethylene compound (2).

(3) Cycloolefin Preparation of resin (COP resin) composition

(3-1) Preparation of cycloolefin resin composition (1)

126 parts by mass of a cycloolefin resin (Polyplastics Co., Ltd., TOPAS (registered trademark) 5013) was added to a mixed solvent of 435 parts by mass of toluene and 439 parts by mass of o-xylene, and further thereto the squarilium compound (A ) 10 parts by mass, 8.4 parts by mass of the ethylene compound (1) obtained in Synthesis Example 1, and 0.52 parts by mass of BYK Japan KK's BYK-330 (polyether-modified polydimethylsiloxane) as a surface modifier, and uniformly mixed. , To obtain a cycloolefin resin composition (1).

(3-2) Cycloolefin Preparation of resin composition (2)

In the preparation example of the above-described cycloolefin resin composition (1), a cycloolefin resin composition (2) was obtained by the same procedure except that the comparative ethylene compound (1) was used instead of the ethylene compound (1).

(3-3) Cycloolefin Preparation of resin composition (3)

In the preparation example of the above cycloolefin resin composition (1), a cycloolefin resin composition (3) was obtained by the same procedure except that the comparative ethylene compound (3) was used instead of the ethylene compound (1).

(4) Preparation of polyarylate resin (PAR resin) composition

(4-1) Polyarylate Resin synthesis

Into a 2 liter reaction vessel equipped with a stirring blade, 10.01 g (0.044 mol) of 2,2'-bis (4-hydroxyphenyl) propane, 3.59 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water were added. After dissolving, 0.89 g (0.009 mol) of triethylamine was added thereto to dissolve. A solution in which 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride were dissolved in 500 g of methylene chloride was placed in a dropping funnel, and this was mounted in the reaction vessel. The solution in the reaction vessel was stirred while maintaining at 20°C, and a methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution in which 0.71 g (0.005 mol) of benzoyl chloride was dissolved in 10 g of methylene chloride was added thereto, followed by stirring for 60 minutes. An aqueous acetic acid solution was added to the obtained reaction solution for neutralization, and the pH of the aqueous phase was set 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 collected 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 number average molecular weight of the polyarylate resin are values in terms of polystyrene calculated by gel permeation chromatography measurement.

(4-2) Polyarylate Preparation of resin composition (1)

100 parts by mass of the polyarylate 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 3.3 parts by mass of the squarilium compound (A) as a near-infrared absorbing dye was added thereto. 1.1 parts by mass of the squarilium compound (B) shown in, 8 parts by mass of the ethylene compound (12) obtained in Synthesis Example 12, and 0.52 parts by mass of BYK Japan KK's BYK-330 (polyether-modified polydimethylsiloxane) as a surface modifier. It was added partly and mixed uniformly, and the polyarylate resin composition (1) was obtained.

(4-3) Polyarylate Preparation of resin composition (2)

100 parts by mass of the polyarylate 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 3.3 parts by mass of the squarilium compound (A) was further added thereto, obtained in Synthesis Example 13. 8.4 parts by mass of the prepared comparative ethylene compound (1), 0.52 parts by mass of BYK Japan KK's BYK-330 (polyether-modified polydimethylsiloxane) as a surface modifier, and uniformly mixed, the polyarylate resin composition (2) was added. Got it.

(4-4) Polyarylate Preparation of resin composition (3)

The polyarylate resin composition (1) obtained above and the hydrolyzed solution of the epoxy group-containing silane coupling agent were uniformly mixed at 25° C. in a mass ratio of the former: the latter = 99:1, and a filter having a pore diameter of 0.1 μm ( A polyarylate resin composition (3) was obtained by filtering with GL Sciences Inc., non-aqueous 13N) to remove foreign matter. In addition, the hydrolysis solution of the epoxy group-containing silane coupling agent includes 24.7 parts by mass of 3-glycidoxypropyltrimethoxysilane (Toray·Dow Corning Corporation., OFS-6040), 32.1 parts by mass of 2-propanol, and 3.4 parts by mass of distilled water. After blending and uniformly mixing at 25°C, 1.54 parts by mass of formic acid was added and mixed for 90 minutes to prepare by advancing the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane.

(4-5) Polyarylate Preparation of resin composition (4)

In the preparation example of the above polyarylate resin composition (3), the squarilium compound (C) shown below as a visible light absorbing dye in place of the squarilium compound (A) and the squarilium compound (B) (Tetrahedron Letters, Vol. 40) , pp.4067-4068 (1999), except for using Product 3a) disclosed in Table 1, and using the ethylene compound (14) obtained in Synthesis Example 14 in place of the ethylene compound (12), polyarylate A polyarylate resin composition (4) was obtained by the same procedure as in the preparation example of the resin composition (3).

(4-6) Polyarylate Preparation of resin composition (5)

In the preparation example of the polyarylate resin composition (3), a polyarylate resin composition (5) was obtained by the same procedure except that the squarilium compound (A) and the squarilium compound (B) were not used.

(4-7) Polyarylate Preparation of resin composition (6)

In the preparation example of the polyarylate resin composition (5), in place of the hydrolysis solution of the epoxy group-containing silane coupling agent, 3-glycidoxypropyltrimethoxysilane (Toray·Dow Corning Corporation., OFS-6040) 24.7 masses A polyarylate resin composition (6) was obtained by the same procedure except that a mixed solution in which 32.1 parts by mass of parts and 2-propanol, 3.4 parts by mass of distilled water and 1.54 parts by mass of formic acid were mixed was used.

(4-8) Polyarylate Preparation of resin composition (7)

In the preparation example of the polyarylate resin composition (4), a polyarylate resin composition (7) was obtained by the same procedure except that the squarylium compound (C) was not used.

(4-9) Polyarylate Preparation of resin composition (8)

In the preparation example of the polyarylate resin composition (3), a polyarylate resin composition (8) was obtained by the same procedure except that the ethylene compound (12) was not used.

(5) Fabrication of optical filter

Each resin composition obtained above was suspended by 2 cc on a glass substrate (Schott, D263 Teco), and then, using a spin coater (MIKASA, 1H-D7), was made 1600 rotations over 0.2 seconds, and for 20 seconds. It was held at the number of rotations, and after that, it was set to 0 rotation for 0.2 seconds (disconnects), and the resin composition was formed into a film on the glass substrate. The glass substrate on which the resin composition was formed was initially dried at 100° C. for 3 minutes using a precision thermostat (Yamato Scientific Co., Ltd., DH611) (before curing). After that, nitrogen was replaced at 50°C for 30 minutes using an inert oven (Yamato Scientific Co., Ltd., DN610I), heated to 190°C in about 15 minutes, and dried at 190°C for 30 minutes in a nitrogen atmosphere. By doing 　, 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. In this way, an optical filter was produced by forming a resin layer on a glass substrate. In addition, the thickness of the resin layer was calculated 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, respectively, and calculated from 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 (Shimadzu Corporation., UV-1800), the absorption spectrum of each ethylene compound in toluene was measured at a measurement pitch of 1 nm, and the transmittance of light at a wavelength of 300 nm to 1100 nm was calculated. The maximum wavelength (λmax) of the maximum absorption peak in the wavelength range of 300 nm to 800 nm was calculated, and the results are summarized in Table 3. In addition, absorption spectra of the ethylene compound (1) and the comparative ethylene compound (1) in toluene are shown in FIG. 1.

(6-2) Measurement of transmission spectrum of optical filter

For each optical filter in which a resin layer was formed on a glass substrate, the transmission spectrum was measured at a measurement pitch of 1 nm using a spectrophotometer (Shimadzu Corporation., UV-1800), and the transmittance of light at a wavelength of 300 nm to 800 nm was calculated. . The transmission spectrum was measured about the optical filter before and after the curing of the resin layer. The results are shown in Figs. 2 to 12.

(6-3) result

As shown in Fig. 1, both the absorption spectra of the ethylene compound (1) and the comparative ethylene compound (1) in toluene showed a maximum absorption peak at a wavelength of about 380 nm. The transmission spectrum of the optical filter formed of an ethylene compound or a resin composition containing an additional squarylium compound is largely changed before and after curing at 190°C, as shown in Figs. 2, 3, 7, 10, and 12. Was not admitted. On the other hand, the transmission spectrum of the optical filter formed of the resin composition containing the comparative ethylene compound and the squarylium compound is as shown in Figs. 4 to 6, 8, 9, and 11, after curing at 190° C. The transmittance of the purple region was 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 exam

81 squares of 4 mm2 were produced by cutting the resin layer of the optical filter obtained above with a cutter (NT Incorporated., A-300) and installing 10 cross-cut lines at 2 mm intervals, respectively, in vertical and horizontal fh. , To prepare a sample substrate for evaluation. A tape (3M company, Scotch (registered trademark) transparent adhesive tape  transparent off-white (registered trademark)) was attached to the sample substrate so that air did not enter, and allowed to stand for 5 seconds. Thereafter, peeling of the tape from the sample substrate was performed within 1 second, and the evaluation was performed according to the following criteria. Moreover, peeling of the tape was performed so that the peeling force might become constant in either of the masses.

A: Of the 81 squares produced, no peeling occurred in even one square.

B: Among the produced 81 squares, peeling occurred in 1 to 9 spaces.

C: Among the produced 81 squares, peeling occurred in 10 to 81 spaces.

(7-2) water After mercy Peeling resistance exam

81 squares of 4 mm2 were produced by cutting the resin layer of the optical filter obtained above with a cutter (NT Incorporated., A-300) and installing 10 crosscuts at 2 mm intervals each in a vertical row and a horizontal row. , To prepare a sample substrate for evaluation. Next, this sample substrate was put in ultrapure water heated to a boiling state, and boiled for 2 hours. Subsequently, at room temperature, a tape (3M company, Scotch (registered trademark), transparent adhesive tape, transparent off-white (registered trademark)) was attached and left for 5 seconds to prevent air from entering. Thereafter, peeling of the tape from the sample substrate was performed within 1 second, and the evaluation was performed according to the following criteria. Moreover, peeling of the tape was performed so that the peeling force might become constant in either mass.

A: Of the 81 squares produced, no peeling occurred in even one square.

B: Among the produced 81 squares, peeling occurred in 1 to 9 spaces.

C: Among the produced 81 squares, peeling occurred in 10 to 81 spaces.

(7-3) result

Table 4 shows the results of the initial peel resistance test and the peel resistance test after boiling with water of the optical filter produced using the polyarylate resin composition (1, 3 to 8). As clearly shown from the results in Table 4, the optical filter formed of the resin composition containing the ethylene compound of the present invention and the silane coupling agent or its hydrolyzed (condensed) product has excellent adhesion between the resin layer and the glass substrate. Became.

(Industrial availability)

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

Claims (10)

Ethylene compound characterized by the following formula (1):

In the above formula, L represents an alkylene group, -O-, -S-, -SO-, a methine group which may have an alkyl group (-C<), a tetravalent linking group of >C< or a linking group that is a combination thereof, a Represents an integer of 2 or more, and A each independently represents a group of the following formula (2):

In the above formula, 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 R ¹ and R ² together are an acyl group, a carboxylic acid ester group or an amide group, 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 ⁴ may be the same or different from each other,
X represents a sulfur atom,
* Indicates the bonding site with the connector (L) of formula (1). The method of claim 1,
The ethylene compound wherein R ² represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group or an amide group. The method according to claim 1 or 2,
An ethylene compound having a maximum absorption peak at a wavelength of 420 nm or less in an absorption spectrum in the range of 300 nm to 600 nm measured in toluene. An ultraviolet absorber containing the ethylene compound according to claim 1. A resin composition comprising the ethylene compound according to claim 1 and a resin component. The method of claim 5,
A resin composition further containing a near-infrared absorbing dye and/or a visible light absorbing dye. The method of claim 5,
Further, a resin composition containing at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolyzate thereof, and a hydrolyzate condensate thereof. A cured product obtained by curing the resin composition according to claim 5. An optical filter comprising the resin composition according to claim 5 or the cured product according to claim 8. A sensor comprising the optical filter according to claim 9.

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