TW201906813A - Vinyl compound, ultraviolet absorber and resin composition - Google Patents

Abstract

An ethylene compound represented by formula (1) and a resin composition comprising the same. (In formula (1): L represents a divalent or higher-valent linking group; a represents an integer greater than or equal to 2; and A independently represents a group shown in formula (2).) (In formula (2): R1 represents a cyano group, an acyl group, a carboxyl group, a carboxylic acid ester group, an amide group or a halogenoalkyl group; R2 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; R1 and R2 may be linked to one another to form a ring; R3 represents a hydrogen atom or an alkyl group; R4 represents a hydrogen atom, an organic group or a polar functional group; X represents a sulfur atom or an oxygen atom; and * represents the site of bonding to the linking group L from 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 resin composition and a cured product thereof, and an optical filter or a sensor including the resin composition.

In the past, various compounds have been known which absorb light in the ultraviolet to purple region. As such compounds, for example, a benzophenone-based compound disclosed in Patent Document 1, a methocyanin-based compound disclosed in Patent Document 2, and a triazine-based compound disclosed in Patent Document 3. 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, or an optical film formed from the resin composition. . [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 7-285927 Patent Document 2: Japanese Patent Application Laid-Open No. 2010-100787 Patent Literature 3: Japanese Patent Application Laid-Open No. 2013-82707 Patent Literature 4: Japanese Patent Application Laid-Open No. 2003-26942 5: Japanese Patent Laid-Open No. 2003-43259

(Invention to solve the problem)

When an ultraviolet absorber is blended in a resin and used as a resin composition, the resin composition can be molded into various shapes according to the intended use. As the use of resin molded products is further expanded, the use for applications requiring heat resistance is also increasing. For example, when an optical filter is formed of a transparent resin, the optical filter can be formed by coating a resin composition on a transparent substrate and then heating it. It can be assembled on an electronic component by solder reflow or by evaporation. A dielectric multilayer film is formed. However, when a UV absorber is contained in the resin composition, the UV absorber must have sufficient heat resistance if it can exhibit desired UV absorption performance even after going through these procedures.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a compound that exhibits absorption peaks in the ultraviolet to purple region and has excellent heat resistance, and a resin composition and an optical filter containing the compound. (Means for solving problems)

The present invention includes the following inventions. [1] an ethylene compound represented by the following formula (1), [In formula (1), L represents a linking group of two or more valences, a represents an integer of two or more, and A each independently represents a group represented by the following formula (2)], [Chemical formula 2] [In formula (2), R ¹ represents a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, a fluorenyl amino group, or a halogenated alkyl group, and R ² represents a hydrogen atom, a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, When fluorenylamino, hydrocarbyl or heteroaryl, when R ¹ and R ^{2 are} both fluorenyl, carboxylate or fluorenyl, R ¹ and R ² may be connected to each other to form a ring, and R ³ represents a hydrogen atom Or 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 as or different from each other, X represents a sulfur atom or an oxygen atom, and * represents a group bonded to the linking group L of formula (1) Parts]. [2] The ethylene compound according to [1], wherein R ² represents a hydrogen atom, a cyano group, a fluorenyl group, a carboxylic acid ester group, or a fluorenylamino group. [3] The ethylene compound according to [1] or [2], wherein an absorption spectrum in a wavelength range of 300 nm to 600 nm measured in toluene has a maximum absorption peak at a wavelength of 420 nm or less. [4] An ultraviolet absorbent containing the ethylene compound according to any one of [1] to [3]. [5] A resin composition containing the ethylene compound according to any one of [1] to [3] and a resin component. [6] The resin composition according to [5], further comprising a near-infrared absorbing dye and / or a visible light absorbing dye. [7] The resin composition according to [5] or [6], further comprising at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolysis product thereof, and a hydrolysis condensation product 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 hardened material according to [8]. [10] A sensor provided with the optical filter according to [9]. (Inventive effect)

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

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

[Chemical 3]

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

[Chemical 4]

In formula (2), R ¹ represents a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, a fluorenyl amino group, or a halogenated alkyl group, and R ² represents a hydrogen atom, a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, or fluorene. In the case of an amine group, a hydrocarbon group or a heteroaryl group, when R ¹ and R ^{2 are} both a fluorenyl group, a carboxylic acid ester group, or a fluorenylamino group, R ¹ and R ² may be connected to each other to form a ring, and R ³ represents a hydrogen atom or 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 as or different from each other, X represents a sulfur atom or an oxygen atom, and * represents a site bonded to the linking group L of formula (1) .

In the group A represented by the formula (2), an ethylene structural unit including R ¹ and R ² functions as a light-emitting group. In the formula (2), as R ¹ and R ² , a cyano group, a fluorenyl group, a carboxyl group, a carboxylate group, a fluorenylamino group, a halogenated alkyl group, a hydrocarbon group, or a heteroaryl group can be used. In formula (2), R ¹ (or R ² ) may be in the ordinal position with respect to R ³ .

Examples of the fluorenyl group (alkylamino) of R ¹ and R ² include methyl fluorenyl, ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, pentyl fluorenyl, hexamethylene, heptyl, octyl, nonyl Decyl, eleven fluorenyl, twelve fluorenyl, thirteen fluorenyl, fourteen fluorenyl, fifteen fluorenyl, hexamer fluorenyl, seventeen fluorenyl, octadecyl fluorenyl, nineteen fluorenyl, Twenty cents. The fluorenyl group may have a part of hydrogen atoms substituted with an aryl group, an alkoxy group, a halogenated group, a hydroxyl group, and the like. The alkyl group in the fluorenyl group may be linear or branched. The carbon number of the fluorenyl group (the number of carbons except for the substituent) is preferably 2 to 21, more preferably 2 to 11, and even more preferably 2 to 6.

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

Examples of the alkyl group of R ¹¹ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, third butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, and the like. Octyl, nonyl, decyl, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, etc. Chain or branched alkyl groups; cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. . An alkyl group may have a part of hydrogen atoms substituted with an alkoxy group, an aryl group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The carbon number of the alkyl group (the number of carbons excluding the substituent) is preferably from 1 to 20. Specifically, if it is a linear or branched alkyl group, the carbon number is preferably from 1 to 20, and more preferably from 1 to 20. 10, more preferably 1 to 5, and in the case of a cyclic alkyl group, 4 to 10 carbon atoms are preferable, and 5 to 8 is more preferable.

Examples of the aryl group of R ¹¹ include phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, and indenyl. An aryl group may have a part of hydrogen atoms substituted with an alkyl group, an alkoxy group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The carbon number of the aryl group (the number of carbons excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

Examples of the aralkyl group of R ¹¹ include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenpentyl, and naphthylmethyl. The aryl group contained in the aralkyl group may have a part of hydrogen atoms substituted with an alkyl group, an alkoxy group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The carbon number of the aralkyl group (carbon numbers other than the substituent) is preferably 7 to 25, and more preferably 7 to 15.

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

When R ¹ and R ^{2 are} both fluorenyl groups, R ¹ and R ² may be connected to each other to form a ring. As a group formed by R ¹ and R ² in this case, the formula is: * -C (= The base is represented by O) -R ¹⁴ -C (= O)-*. In the formula, R ¹⁴ represents a linear or branched alkylene group, and * represents a bonding site to a carbon atom of the ethylene double bond of the formula (2). An alkylene group may have a part of hydrogen atoms substituted with an aryl group, an alkoxy group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The carbon number of the alkylene group of R ¹⁴ (the number of carbons excluding the substituent) is preferably 2 to 10, and more preferably 3 to 8. Examples of the group (cyclic group) formed by bonding the fluorenyl 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 carboxylic acid ester groups, R ¹ and R ² may be connected to each other to form a ring. The group formed by R ¹ and R ² in this case is represented by the formula: *- The bases represented by C (= O) -OR ^15- OC (= O)-*. In this formula, R ¹⁵ represents a linear or branched alkylene group, and * represents a bonding site to a carbon atom of the ethylene double bond of the formula (2). An alkylene group may have a part of hydrogen atoms substituted with an aryl group, an alkoxy group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The number of carbons (the number of carbons excluding the substituent) of the alkylene group of R ¹⁵ is preferably 1 to 8, more preferably 1 to 6. Examples of the group (cyclic group) formed by connecting 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 amidino group, R ¹ and R ² may be connected to each other to form a ring. As a group formed by R ¹ and R ² in this case, the formula is: * -C ( = O) -NR ¹⁶ -R ¹⁷ -NR ¹⁸ -C (= O)-*. In the formula, R ¹⁶ and R ¹⁸ represent a hydrogen atom or a hydrocarbon group, R ¹⁷ represents a linear or branched alkylene group, or a carbonyl group, and * represents a carbon atom bonding site for the ethylene double bond of the formula (2). . Preferred examples of the hydrocarbon group of R ¹⁶ and R ¹⁸ include an alkyl group, an aryl group, and an aralkyl group. For specific examples of the alkyl group, aryl group, and aralkyl group of R ¹⁶ and R ¹⁸ , refer to the description of the alkyl group, aryl group, and aralkyl group of R ¹¹ described above. The alkylene group of R ¹⁷ may have a part of hydrogen atoms substituted with an aryl group, an alkoxy group, a cyano group, a halogenated group, a hydroxyl group, a nitro group, or the like. The carbon number of the alkylene group of R ¹⁷ (the number of carbons excluding the substituent) is preferably 1 to 8, and more preferably 1 to 6. Examples of the group (cyclic group) formed by linking the amido groups of R ¹ and R ² to each other include a group represented by the following formula (3-3) and formula (3-4).

[Chemical 5]

Examples of the halogenated alkyl group of R ¹ include those in which a part or all of the hydrogen atoms of the alkyl group of R ¹¹ described above are 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 of R ² include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group). The aliphatic hydrocarbon group may be either saturated or unsaturated, or may be linear, branched, or cyclic. For specific examples of the aliphatic saturated hydrocarbon group, refer to the description of the alkyl group of R ¹¹ described above. Specific examples of the aliphatic unsaturated hydrocarbon group include the carbon-carbon single bond of the R ¹¹ alkyl group which has been described above as a double bond. Or three-button. For specific examples of the aromatic hydrocarbon group (aryl group), refer to the description of the aryl group of R ¹¹ described above. As the hydrocarbon group of R ² , an aryl group is preferred.

Examples of the heteroaryl group of R ² include thienyl, thianyl, isothiobenzopiperanyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrrolidinyl, pyrimidinyl, and daphthyl , Thiazolyl, isothiazolyl, furyl, piperanyl, and the like. Moreover, the heteroaryl group is preferably a carbon atom bonded to a carbon atom of the ethylene double bond of the formula (2), and a carbon atom adjacent to the hetero atom is preferably bonded to a carbon atom of the ethylene double bond of the formula (2). This makes it easier to synthesize ethylene compounds. The carbon number of the heteroaryl group is preferably 3 to 18, and more preferably 4 to 12.

In formula (2), R ^{2 is} preferably a hydrogen atom, a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, or a fluorenylamino group. In this way, it is easy to effectively absorb light in the ultraviolet to purple region. In the case where the wavelength is set to be longer than the absorption peak of the ethylene compound, for example, not only the entire ultraviolet region but also the light in the wavelength region of 350 nm to 420 nm, R ^{2 is} not a hydrogen atom. Better.

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

In the group A represented by formula (2), the benzene ring system connected to the ethylene structure part and the X (sulfur atom or oxygen atom) connected to the benzene ring both serve to supply electrons to the ethylene structure part. The absorption wavelength of the luminescent group is adjusted to the ultraviolet to purple region. R ⁴ bonded to the benzene ring represents a hydrogen atom, an organic group, or a polar functional group, and a plurality of R ⁴ may be the same as or different from each other.

Examples of the organic group of R ⁴ in the formula (2) include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkanesulfonyl group, an alkanesulfinyl group, an aryl group, an aralkyl group, and an aryloxy group. Group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, arylsulfinyl group, heteroaryl group, amine group, fluorenylamino group, sulfonamido group, carboxyl (carboxylic acid group), cyano group, and the like. Examples of the polar functional group of R ⁴ include a halogenated group, a hydroxyl group, a nitro group, and a sulfo group (sulfonic acid group).

For specific examples of the alkyl group of R ⁴ , refer to the description of the alkyl group of R ¹¹ described above. The alkyl group of R ⁴ may have a substituent. Examples of the substituent of the alkyl group include an aryl group, a heteroaryl group, a halogenated group, a hydroxyl group, a carboxyl group, an alkoxy group, a cyano group, a nitro group, and an amine group. , Sulfo and so on.

R ⁴ is an alkoxy group, an alkylthio group, an alkoxycarbonyl group, a sulfo alkyl acyl, alkoxy specific examples of the alkyl sulfinyl group contained in the reference description of the alkyl group for R ^4.

Specific examples of the aryl group and the aralkyl group of R ⁴ refer to the description of the aryl group and the aralkyl group of R ¹¹ described above. The aryl group of R ⁴ or the aryl group included in the aralkyl group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a heteroaryl group, a halogenated group, a halogenated alkyl group, a hydroxyl group, and a cyanide. Nitro, amine, thio, thiocyano, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, sulfinyl, sulfinyl, sulfinyl, sulfonyl, sulfonyl Fluorenyl, sulfamoyl and the like.

R ⁴ is an aryloxy group, an arylthio group, an aryloxycarbonyl group, an aryl sulfonic acyl, specific examples of the aryl sulfinyl group, an aryl group included in R based on the aryl group described with reference ^4.

Specific examples of the heteroaryl group of R ⁴ refer to the above description of the heteroaryl group of R ² . The heteroaryl group may have a substituent. Examples of the substituent having a heteroaryl group include an alkyl group, an alkoxy group, an aryl group, a halogenated group, a halogenated alkyl group, a hydroxyl group, a cyano group, an amine group, a nitro group, and a sulfur group. Cyano, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfinyl, arylsulfinyl, aminesulfinyl, and the like.

The amine group of R ⁴ is represented by the formula: -NR ²¹ R ²² , and R ²¹ and R ²² can be independently listed as hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, and heteroaryl group. . Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group are as described above. Examples of the alkenyl group and alkynyl group include a carbon-carbon single bond in which an alkyl group is partially substituted with a double or triple bond A substituent of a bond. These substituents may also be substituted by a halogen atom as a part of the hydrogen atom. In addition, R ²¹ and R ²² may be connected to each other to form a ring.

As the acyl group R ⁴ of the formula: -NH-C (= O) -R 23 represent, R ²³ include alkyl, aryl, arylalkyl, heteroaryl persons. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group refer to the above description, and a part of hydrogen atoms may be substituted with a halogen atom.

As the sulfonylurea group R ⁴ to the formula: -NH-SO ₂ -R ²⁴ represent, R ²⁴ include alkyl, aryl, arylalkyl, heteroaryl persons. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group refer to the above description, and a part of hydrogen atoms may be substituted with a halogen atom.

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

R ^{4 is} preferably one or more selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group, and an arylthio group. For example, when R ⁴ is a nitrogen-containing substituent, the substituent R ⁴ is decomposed by heating, reaction, or the like, and is converted into another structure. The ethylene compound is liable to exhibit a color such as yellow, which is not preferable. From the viewpoint that the ethylene compound can stably absorb light in the ultraviolet to purple region, R ⁴ is preferably a hydrogen atom or an alkyl group, and the alkyl group is preferably a carbon number of 1 to 4 and more preferably 1 to 3. In particular, among the four R ⁴ bonded to the benzene ring of the group A of the formula (2), 2 or more are preferably hydrogen atoms, 3 or more are preferably hydrogen atoms, and 4 of them are most preferably hydrogen atoms. .

X in the formula (2) represents a sulfur atom or an oxygen atom. As a result, the ethylene compound easily and stably absorbs light in the ultraviolet to purple region. From the viewpoint of being able to efficiently absorb light in the UV region, X is preferably a sulfur atom.

In the group A represented by the formula (2), X may be bonded to an ortho position with respect to the vinyl structural part, or may be bonded to a para position, and may be bonded to a para position. From the standpoint of ease of production of the ethylene compound, X is preferably bonded to the para structure with respect to the ethylene structure.

In formula (1), two or more groups A are bonded to the linking group L. When two or more groups A are bonded 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 the groups A bonded to the linking group L of formula (1) is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. From the viewpoint of easily producing a highly stable ethylene compound, a is preferably 3 or less, and more preferably 2.

Examples of the linking group L include divalent links such as alkylene, arylene, heteroarylene, -O-, -CO-, -S-, -SO-, -SO _2- , and -NH-. A trivalent linking group which may have an alkyl group (-C <), -N <and the like; a tetravalent linking group having> C <the equivalent; and a linking group combining these. The alkylene group may be any of linear, branched, and cyclic. In addition, the alkylene group and the arylene group may have a hydroxyl group and / or a mercapto group.

Examples of the linking group L include groups represented by the following formulae (4-1) to (4-17). In the formulae (4-1) to (4-17), * represents a binding site of the group A. Two groups A are bonded to the linking group L of Formulas (4-1) to (4-9), and three groups A are bonded to the linking group L of Formulas (4-10) to (4-13). Four groups A are bonded to the linking group L of formula (4-14) to formula (4-15), five groups A are bonded to formula (4-16), and six groups are bonded to formula (4-17). Radical A.

[Chemical 6]

From the viewpoint of improving the stability of the ethylene compound, the linking group L is an alkylene group in which a part of hydrogen atoms may be substituted by a hydroxyl group and / or a thiol group, a part of hydrogen atoms may be substituted by a hydroxyl group and / or a thiol group, and -O -, -S-, and a linking group in which these groups are combined are preferred (however, ether bonding and thioether bonding are discontinuous). In addition, the number of carbon atoms (continuous carbon number) of the linear or branched alkylene group is preferably 6 or less, 4 or less is more preferable, and 3 or less is more preferable. In the case of a cyclic alkylene group, a carbon number of 4 or more is preferable, 5 or more is more preferable, and 10 or less is more preferable, and 8 or less is more preferable. The number of carbon atoms of the arylene group is preferably 5 or more, 6 or more is more preferable, and 10 or less is more preferable, and 8 or less is more preferable.

The ethylene compound is preferably an ethylene compound represented by the following formula (5). Such an ethylene compound has, for example, a peak having a maximum absorption in a wavelength range of 300 nm to 420 nm, and can effectively absorb light in the ultraviolet to purple region, and has good stability and ease of manufacture. In the following formula (5), the description of R ^1a and R ^1b refers to the description of R ¹ described above, the description of R ^2a and R ^2b refers to the description of R ² described above, and the description of R ^3a and R ^3b refers to the description of R ³ described above. For the description of X ^a and X ^b , refer to the description of X above.

[Chemical 7]

The ethylene compound of the present invention has an absorption spectrum in a wavelength range of 300 nm to 600 nm (preferably in a range of 300 nm to 700 nm, more preferably in a range of 300 nm to 800 nm) measured in toluene. Those with a maximum absorption peak below 420 nm are preferred. In other words, when the absorption spectrum of the ethylene compound in toluene is measured, it has a peak having a maximum absorption in a wavelength range of 300 nm to 420 nm, and it is preferable that the maximum absorption system of the absorption peak is in a range of 300 nm to 600 nm. The maximum value. If the ethylene compound exhibits such an absorption spectrum, it becomes a person capable of effectively absorbing light in the ultraviolet to purple region. The maximum wavelength of the absorption peak is preferably 310 nm or more, more preferably 315 nm or more, more preferably 410 nm or less, and 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 when the absorbance of the absorption peak is 0.5 is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less. If the ethylene compound exhibits such an absorption spectrum, it will be able to selectively absorb light in the ultraviolet to purple region. The lower limit value of the peak width is not particularly limited, but may be, for example, 20 nm or more and 30 nm or more.

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

The absorption spectrum is obtained by measuring the absorbance at a measurement interval of 1 nm in a predetermined wavelength range. The value of the absorbance at the wavelength when the measurement pitch (1 nm) is not reached is calculated from the measured value of the absorbance at the 1 nm pitch by linear interpolation. The absorbance of the concentration of the ethylene compound in toluene at the maximum absorption of the maximum absorption peak was adjusted to 1 ± 0.003. The average absorbance in the range of 470 nm to 600 nm is obtained by averaging the absorbance values at 131 points measured at a 1 nm pitch in the range of 470 nm to 600 nm.

Since the ethylene compound of the present invention can effectively absorb light in the ultraviolet to purple region, it is suitable for use as an ultraviolet absorbent. The ethylene compound can be used by dissolving or dispersing it in any solvent (for example, water, organic solvent, etc.). Therefore, the ultraviolet absorbent may be one containing a solvent.

The vinyl compound contained in the ultraviolet absorber may be only one kind, or two or more kinds. The ultraviolet absorbent may include a known ultraviolet absorbent other than the vinyl compound of the present invention (for example, benzotriazole-based compounds, benzophenone-based compounds, salicylic acid-based compounds, benzoxazinone-based compounds, cyanide Acrylate-based compounds, benzoxazole-based compounds, merocyanin-based compounds, triazine-based compounds, etc.).

The ethylene compound of the present invention can be produced in accordance with the procedure shown below, for example. In the following scheme, R ¹ to R ³ , X, and L have the same meanings as in the above formula (1), and their preferred aspects are as described above. Y represents a halogen atom. In addition, the group R ⁴ is omitted in the following description, and a compound using a divalent linking group as the linking group L is used as an example.

[Chemical 8]

First, by reacting a compound of formula (6) that provides a precursor of group A with a compound of formula (7) that provides a linking group L, a formula in which a precursor of group A is bonded to both ends of the linking group L can be obtained. (8) The compound. The compound of the formula (6) is a halogenated phenyl ketone compound or a halogenated phenyl aldehyde compound. The compound of the formula (6) may be used alone or in combination of two or more. The compound of formula (7) is a compound having a hydroxyl group and / or a mercapto group. By reacting a compound of formula (6) with a compound of formula (7), X (sulfur atom or oxygen atom) of the compound of formula (7) nucleophiles the carbon atom of the halogen atom of the compound of formula (6) The compound can be obtained as a compound of formula (8) in which the precursor of the group A is bonded to the linking group L.

As the compound (7), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanedithiol, 1,2-propylenedithiol, 2-mercaptoethanol, and thiodiethyl can be used. Diols, bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, 1,3-bis (2-mercaptoethylthio) propane, cyclohexanediol, hydroquinone, bisphenol A and other compounds that provide a divalent linking group L; glycerol, dimercaptopropanol, cyclohexanetriol, pyrogallol, trimethylolpropane trimercaptoacetate, trimethylolpropane ginseng (3-mercaptopropionic acid Esters), ginseno-[(3-mercaptopropoxy) -ethyl] -isocyanurate, and other compounds that provide a trivalent linking group L; butaerythritol, pentaerythritol tetramercaptoacetate, pentaerythritol tetra ( 3-mercaptopropionate) and other compounds providing a tetravalent linking group L; ribitol, such as compounds providing a 5-valent linking group L; dipentaerythritol hexamercaptoacetate, dipentaerythritol hexa (3-mercaptopropionate) Compounds that provide a hexavalent linking group L and the like.

Next, the compound of the formula (8) and the compound of the formula (9) are subjected to a Knoevenagel condensation reaction to obtain the ethylene compound of the present invention of the formula (10). When the methylene group between R ¹ and R ² is held by a cyano group and / or a carbonyl group, the compound of the formula (9) is particularly highly reactive with the carbonyl group of the compound of the formula (8). The compound of formula (9) may be used singly or in combination of two or more kinds.

As the compound (9), acetonitrile, propionitrile, malononitrile, phenyl acetate, cyanoacetate, malonic diester, 2-cyano-N, N-dimethylacetamide, and N-formyl can be used. Ethyl acetamidine, acetamidine aniline, N, N, N ', N'-tetramethylpropanediamine, 1,3-cyclohexanedione, bismethanone, Mie acid, barbi Tartrate and so on.

The above reaction is preferably performed in the presence of a solvent. Examples of usable solvents include chlorine-based hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene, xylene, and xylene; chlorine-based aromatics such as chlorotoluene and dichlorobenzene; and tetrahydrofuran ( THF), dioxane, cyclopentyl methyl ether, diisopropyl ether, diethyl ether and other ethers; nitriles such as acetonitrile, propionitrile, acrylonitrile, and butyronitrile; alcohols such as methanol, ethanol, propanol, and butanol ; Formic acid, acetic acid, propionic acid and other organic acids. These solvents may be used alone or in combination of two or more.

In the above reaction, the reaction temperature may be appropriately set. For example, 0 ° C or higher, 5 ° C or higher, 10 ° C or higher, or 200 ° C or lower, or 150 ° C or lower is preferable. This reaction can also be performed under reflux. The reaction time is not particularly limited, and the progress of the reaction may be appropriately set. However, for example, 0.5 hours or more is preferable, 1 hour or more is preferable, 48 hours or less is preferable, and 24 hours or less is preferable. The environment gas at the time of the reaction is preferably performed under an inert gas (nitrogen, argon, etc.) environment gas during the production reaction of the compound of the formula (8).

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

The ethylene compound of the present invention is mixed with a resin component to form a resin composition. Since the ethylene compound of the present invention is excellent in heat resistance, for example, it is blended in a thermoplastic resin, and even when it is heat-formed, the ultraviolet absorption effect can be appropriately exhibited. In addition, the resin composition containing the ethylene compound of the present invention can suppress deterioration due to light in the ultraviolet to purple region, and at the same time, it can be used as a resin that cuts light in the ultraviolet to purple region because it is cured into a resin molded body such as a film. Optical filters, etc. In addition, during storage of the resin composition, resin molded body, etc., during manufacture and processing of optical filters (e.g., vapor deposition, mounting, etc.), etc., even if exposed to ultraviolet light, the resin component, resin composition, etc. are protected. The other components (near-infrared absorbing pigments and the like described later) contained in this are free from this ultraviolet light, and deterioration of these components can be suppressed.

The resin composition includes at least the ethylene compound and the resin component of the present invention. There may be only one vinyl compound or two or more vinyl compounds contained in the resin composition. The resin composition may further contain other ultraviolet absorbers (for example, benzotriazole-based compounds, benzophenone-based compounds, salicylic acid-based compounds, benzoxazinone-based compounds, cyanoacrylate-based compounds, benzo Oxazole-based compounds, merocyanin-based compounds, triazine-based compounds, etc.).

The content of the ethylene compound in the resin composition is, from the viewpoint of exhibiting desired performance, of 100% by mass of the solid content of the resin composition, preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and 0.1% by mass. The above is better. In addition, from the viewpoint of improving the moldability and film-forming property of the resin composition, the content of the vinyl compound in the resin composition is preferably 25% by mass or less in 100% by mass of the solid content of the resin composition. 20% by mass or less is preferable, and 15% by mass or less is more preferable. When the resin composition contains other ultraviolet absorbers, the total content is preferably within the above range. In addition, the content of other ultraviolet absorbers is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the ethylene compound. The solid content of the resin composition means the amount of the resin composition other than 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 the resin component, those having high transparency and capable of dissolving or dispersing the ethylene compound of the present invention are preferred. When the resin composition also contains a near-infrared absorbing dye, a visible light absorbing dye, and the like 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 have both high transmittance in the wavelength region to be penetrated and high absorptivity in the wavelength region to be masked.

As the resin component, not only the resin that has been polymerized, but also resin materials (including a precursor of the resin, a raw material of the precursor, a monomer constituting the resin, etc.) may be used. When the resin composition is molded, a polymerization reaction or a crosslinking reaction is performed. Mix to resin. In the present invention, any resin is included in the resin component. In the latter case, it is possible to make a part or all of the unreacted substances, reactive terminal functional groups, ionic groups, catalysts, acids, basic groups, etc. present in the reaction solution obtained by the polymerization reaction. Structural decomposition of vinyl compounds. Therefore, when there is such a doubt, it is desirable to formulate the resin after polymerization to an ethylene compound to form a resin composition.

As the resin component, it is preferable to use a resin having high transparency. In this way, the characteristics of the ethylene compound contained in the resin composition can be appropriately utilized. Examples of the resin component include (meth) acrylic resin, urethane (meth) acrylate resin, polyvinyl chloride resin, polyvinylidene chloride resin, and polyolefin resin (such as polyethylene resin and polypropylene resin). ), Cycloolefin resin, melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (such as nylon), polyaramide resin, polyimide resin, polyimide Amine resin, alkyd resin, phenol resin, epoxy resin, polyester resin (e.g. polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, polyarylate resin Etc.), polyfluorene resin, butyraldehyde resin, polycarbonate resin, polyether resin, ABS resin (acrylic acryl-butadiene styrene resin), AS resin (acrylic acryl-styrene copolymer), silicone resin, Modified silicone resins (e.g. (meth) acrylic silicone resins, alkyl polysiloxane resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc.), fluorine resins (e.g. Fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxyfluoro Fat (PFA), fluorinated poly aryl ether ketone (FPEK), fluorinated poly Amides (FPI), fluorinated polyamide acid (FPAA), fluorinated polyether nitrile (FPEN), etc.) and the like. Among these, from the viewpoints of good transparency and heat resistance, polyimide resins, polyimide resins, (meth) acrylic resins, cycloolefin resins, epoxy resins, Polyester resin, polyarylate resin, polyamide resin, polycarbonate resin, polyfluorene resin, and fluorinated aromatic polymer are preferred.

Polyimide resin-based polymers containing polyimide bonds in the repeating units of the main chain of polyimide resins can be dehydrated and cyclized by, for example, polyamic acid obtained by polycondensation of tetracarboxylic acid 2 anhydride and diamine. Sulfonation (imidization). As the polyimide resin, it is preferable to use an aromatic polyimide in which an aromatic ring is linked by a imidate bond. As the polyimide resin, for example, Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Kapton (registered trademark) manufactured by DuPont, AURUM (registered trademark) manufactured by Mitsui Chemicals, or MELDIN (registered trademark) manufactured by Saint-Gobain Trademark), TPS (registered trademark) TI3000 series manufactured by Toray Plastics Precision Co., Ltd., etc.

The repeating unit of the polyamidoamidine resin-based main chain contains a polyamidoamine-bonded and a polyamidoamine-bound polymer. As the polyamidoamine resin, for example, TORLON (registered trademark) manufactured by Solvay Advanced Polymers, Vylomax (registered trademark) manufactured by Toyobo Corporation, TPS (registered trademark) TI5000 series manufactured by Toray Plastics Precision Co., Ltd. can be used. .

The (meth) acrylic resin is a polymer having a repeating unit derived from (meth) acrylic acid or a derivative thereof. For example, a poly (meth) acrylate resin or the like having a repeating unit derived from (meth) acrylate can be preferably used. Unit of resin. The (meth) acrylic resin preferably has a ring structure in the main chain, and examples thereof include a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, and a maleimide ring structure. And other carbonyl group-containing ring structures; propylene oxide ring structure, trimethyleneimine ring structure, tetrahydrofuran ring structure, pyrrolidine ring structure, tetrahydropiran ring structure, piperidine ring structure and other ring structures without carbonyl group. In addition, the ring structure containing a carbonyl group also includes a structure containing a carbonyl derivative group such as a fluorenimine group. As the (meth) acrylic resin having a carbonyl group-containing ring structure, for example, Japanese Patent Laid-Open No. 2004-168882, Japanese Patent Laid-Open No. 2008-179677, International Publication No. 2005/54311, and Japanese Patent Laid-Open No. 2007-31537 can be used. Those listed in the bulletin.

The cycloolefin-based resin is not particularly limited as long as it is a polymer obtained by polymerizing such a cycloolefin as at least a part of the monomer component, as long as it has an alicyclic structure in a part of the main chain. As the cycloolefin-based resin, for example, TOPAS (registered trademark) manufactured by POLYPLASTICS Corporation, APEL (registered trademark) manufactured by Mitsui Chemicals Corporation, ZEONEX (registered trademark) and Zeonor (registered trademark) manufactured by Zeon Corporation, and JSR Corporation can be used. ARTON (registered trademark), etc.

The epoxy resin is a resin in which an epoxy compound (prepolymer) is cross-linked in the presence of a curing agent, a curing catalyst, and the like, and is cured. 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, a fluorene-based epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd.) can be used. OGSOL (registered trademark) PG-100), bisphenol A type epoxy compound (JER (registered trademark) 828EL) manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy compound (JER (registered trademark) YX8000), etc., Daicel The company's alicyclic epoxy compound (EHPE (registered trademark) 3150), a bifunctional alicyclic epoxy compound (CELLOXIDE (registered trademark) 2021P), and the like.

The polyester resin is a polymer containing an ester bond in a repeating unit of the main chain, and can be obtained, for example, by polycondensation of a polycarboxylic acid (dicarboxylic acid) and a polyhydric alcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. As the ester, for example, OKP series manufactured by Osaka Gas Chemical Co., TRN series manufactured by Teijin Corporation, Teonex (registered trademark), Rynite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Mitsubishi Novaduran (registered trademark) manufactured by Engineering Plastics Corporation, Lumirror (registered trademark) manufactured by Toray Corporation, Toraycon (registered trademark), Elitel (registered trademark) manufactured by Unitika Corporation, and the like.

Polyarylate resin is a polymer obtained by the polycondensation of a divalent phenol compound with a diprotic acid (such as an aromatic dicarboxylic acid such as phthalic acid). The polymer has a repeat that contains an aromatic ring and an ester bond in the repeating unit of the main chain. unit. As the polyarylate resin, for example, vectran (registered trademark) manufactured by Kuraray Corporation, UPOLYMER (registered trademark) manufactured by Unitika Corporation, UNIFINER (registered trademark), or the like can be used.

Polyamine resin is a polymer containing an amine bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing a diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in the main chain. As such a polyamide resin, for example, nylon may be used. The polyamide resin may be one having an aromatic skeleton. As such a polyamide resin, a polyarylamine resin is known. From the viewpoint of good heat resistance and strong mechanical strength, Taraon (registered trademark), Conex (registered trademark), and Kevlar (registered trademark) made by DuPont are preferably used for the polyaramide resin. , Nomex (registered trademark), etc.

Polycarbonate resin is a polymer containing a carbonate group (-O- (C = O) -O-) in a repeating unit of the main chain. As the polycarbonate resin, Panlite (registered trademark) manufactured by Teijin Corporation, Iupilon (registered trademark), NOVAREX (registered trademark), XANTAR (registered trademark), Sumika Styron Polycarbonate Limited, SD POLYCA (Registered trademark), etc.

The polyfluorene resin is a polymer having a repeating unit containing an aromatic ring, a fluorene group (-SO _2- ), and an oxygen atom. As the polyfluorene resin, for example, SUMIKAEXCEL (registered trademark) PES3600P or PES4100P manufactured by Sumitomo Chemical Co., Ltd., and UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers can be used.

The fluorinated aromatic polymer has an aromatic ring having one or more fluorine atoms, and is selected from the group consisting of an ether bond, a ketone bond, a fluorene bond, a fluorene amine bond, a fluorene amine bond, and an ester bond. The polymer of the group having at least one bonded repeating unit is preferably a polymer which must contain an aromatic ring having at least one fluorine atom and an ether bonded repeating unit. As the fluorinated aromatic polymer, for example, those described in Japanese Patent Application Laid-Open No. 2008-181121 can be used.

The resin component is preferably high in transparency, so that the resin composition can be easily applied to optical applications. For example, 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 more preferably 85% or more. The upper limit of the total light transmittance of the resin component is not particularly limited. However, if the total light transmittance is 100% or less, for example, 95% or less may be sufficient. The total light transmittance is measured based on JIS K 7105.

The resin component preferably has a high glass transition temperature (Tg). In this way, it is possible to improve the heat resistance of the resin composition and the various molded bodies obtained thereby. The glass transition temperature of the resin component is preferably 110 ° C or higher, more preferably 120 ° C or higher, and more preferably 130 ° C or higher. Although the upper limit of the glass transition temperature of a resin component is not specifically limited, From a viewpoint of ensuring the moldability of a resin composition, it is preferable that it is 380 degreeC or less, for example.

The resin composition may contain a near-infrared absorbing pigment and / or a visible light absorbing pigment. If the resin composition further contains a near-infrared absorbing pigment and / or a visible light absorbing pigment, an optical filter having light selective transmittance can be obtained from the resin composition. For example, if the resin composition contains the ethylene compound and the near-infrared absorbing pigment of the present invention, it can selectively penetrate as light that suppresses light penetration in the ultraviolet-violet region and red-near-infrared region, and preferentially transmits light in the visible region. The resin composition for a filter is used. When the resin composition contains the ethylene compound of the present invention and a visible light absorbing dye, the resin composition can be used as a resin composition for a color filter, a blue light reduction filter, or the like.

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

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

The near-infrared absorbing dye and the visible light absorbing dye may be organic dyes, inorganic dyes, or organic-inorganic composite dyes (for example, organic compounds having a metal atom or an ion coordination), and are not particularly limited. Examples of near-infrared absorbing pigments and visible light absorbing pigments include, for example, squaric acid pigments, ketocyanine pigments, and copper (for example, Cu (II)), zinc (for example, Zn (II)), etc. as the central metal ion. Cyclic tetrapyrrole pigments (porphyrins, chlorins, peptides, naphthocyanines, cholines, etc.), anthocyanins, azo pigments, quinone pigments, xanthene Pigments, indolinoline pigments, arylmethane pigments, quaterrylene pigments, diimmonium salt pigments, fluorene pigments, quinacridone pigments, fluorene pigments, Pyrrole methane dyes, nickel complex dyes, copper ion dyes, and the like. These pigments may be used alone or in combination of two or more. Among them, from the viewpoint of efficiently absorbing light of a desired wavelength, as the near-infrared absorbing pigment and the visible light absorbing pigment, at least one selected from the group consisting of anthocyanin-based pigments, squaraine compounds, ketocyanine compounds, and Pyrrole methane pigments and peptide cyanine compounds are preferred. As a near-infrared absorbing pigment, from the viewpoint of efficiently absorbing light in the near-infrared region and easily improving the transmittance of visible light, at least one selected from the group consisting of a squaraine compound, a ketocyanine compound, and a peptide cyanine compound is used. Better.

When the resin composition contains a near-infrared absorbing pigment and / or a visible-light absorbing pigment, the content of the near-infrared absorbing pigment and the visible-light absorbing pigment in the resin composition is a solid state of the resin composition from the viewpoint of exhibiting desired performance. Of 100 parts by mass, 0.01% by mass or more is preferable, 0.03% by mass or more is preferable, and 0.1% by mass or more is more preferable. In addition, from the viewpoint of improving the moldability and film-forming property of the resin composition, the content of the near-infrared absorbing pigment and visible light absorbing pigment in the resin composition is 25% by mass based on 100% by mass of the solid content of the resin composition. % Or less is preferable, 20% by mass or less is preferable, and 15% by mass or less is more preferable. In addition, the total content of the ethylene compound, the near-infrared absorbing pigment, and the visible light absorbing pigment (or the total content of other ultraviolet absorbers) is more preferably 30% by mass or less out of 100% by mass of the solid content of the resin composition. 25 It is preferably less than mass%, and more preferably less than 20 mass%.

When the resin composition is used as a resin composition for a light selective transmission filter that preferentially transmits light in the visible light region, for example, a squaraine compound represented by the following formula (11) is used as a near-infrared absorbing pigment. Or, a ketocyanine compound represented by the following formula (12) is preferred. In the following formulae (11) and (12), R ²¹ to R ²⁴ each independently represent a group represented by the following formula (13) or formula (14).

[Chemical 9]

[Chemical 10]

In formula (13), ring P represents an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing such a ring structure, and R ³¹ to R ³³ each independently represent a hydrogen atom, an organic group, or A polar functional group, R ³² and R ³³ may be bonded to each other to form a ring. In 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 , and R ³⁷ and R ³⁸ are respectively They may be connected to each other to form a ring. * Represents the site where the 4-membered ring in formula (11) or the 5-membered ring in formula (12) is bonded.

The detailed description of the organic groups and polar functional groups of R ³¹ to R ³⁸ is made with reference to the description of the organic groups and polar functional groups of R ⁴ described above. When R ³¹ to R ³⁸ are independent groups, it is preferable that R ³¹ to R ³⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an amine group, an amidino group, or a hydroxyl group. For a detailed description of these groups, reference is made to the description of R ⁴ above.

Examples of the ring structures formed by R ³² to R ³⁸ include a hydrocarbon ring and a heterocyclic ring. These ring structures may or may not have aromaticity, but are non-aromatic hydrocarbon rings or non-aromatic heterocyclic rings. Better. Examples of the non-aromatic hydrocarbon ring include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; cyclopentene, cyclohexene, cyclohexadiene (for example, 1,3-cyclohexadiene), and a ring Cycloolefins such as heptene and cycloheptadiene. Examples of the non-aromatic heterocyclic ring include at least one carbon atom selected from the group consisting of N (nitrogen atom), S (sulfur atom), and O (oxygen atom). The ring replaced by the above atom. Examples of the non-aromatic heterocyclic ring include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropiperan ring, a tetrahydrothioan ring, a morpholine ring, a hexamethyleneimine ring, An epoxy hexane ring, a cyclohexane sulfide ring, an azacyclooctane ring, and the like.

Among the groups of formula (13), as the ring structure formed by the connection between R ³² and R ³³ , a 4- to 9-membered unsaturated hydrocarbon ring is preferred, and among them, cyclopentene, cyclohexene, cycloheptene, and cyclo Cycloalkane monoenes such as octene are preferred. The base of the formula (13) constructed in this way reduces the shoulder of the absorption waveform in the red to near-infrared region and becomes the steepest absorption peak.

Examples of the aromatic hydrocarbon ring of the ring P of the formula (13) include a benzene ring, a naphthalene ring, a phenanthrene ring, an onion ring, a fluoranthene ring, and a roene ring. The aromatic hydrocarbon ring may have only one ring structure, or may be formed by condensing two or more ring structures. The aromatic heterocyclic ring of ring P contains one or more atoms selected from the group consisting of N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in the ring structure. The aromatic ring includes, 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 tick ring, a pyrimidine ring, a pyridine ring, a purine ring, a pyrimidine ring, and the like. The aromatic heterocyclic ring may be one having only one ring structure, or may be obtained by condensing two or more ring structures. Examples of the condensed ring system having such a ring structure including the ring P include an aromatic hydrocarbon ring and an aromatic heterocyclic condensed ring. Examples include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, and benzene. Pyridine ring, acridine ring, xanthene ring, carbazole ring and the like. By appropriately setting the π conjugate system of the 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 an organic group and a polar functional group as described above. When ring P has a substituent, its number is preferably from 1 to 3, more preferably from 1 to 2, and even more preferably from 1. The ring P may not have a substituent.

The detailed description of the squaraine compound and the ketocyanine compound having a group of the formula (13) is described in Japanese Patent Application Laid-Open No. 2016-74649.

In the group represented by formula (14), R ³⁵ and R ^{36 are} preferably connected to form a ring, and R ³⁶ and R ³⁷ may be connected to form a ring. At this time, at least R ³⁴ and R ³⁸ are independent groups. In the base of the formula (14) thus constituted, the absorption peak in the red to near-infrared region becomes steep. In addition, the number of ring members such as the ring structure formed by R ³⁵ and R ³⁶ and the ring structure formed by R ³⁶ and R ³⁷ is preferably 5 or more, 6 or more is preferable, and 12 or less is preferable, 10 The following is preferable, and 8 or less is more preferable.

The group represented by the formula (14) preferably uses R ³⁶ as an amine group, and R ³⁶ as the amine group is connected to R ^{35 to} form a ring, and R ^{37 is} also preferably connected to form a ring. At this time, the maximum absorption wavelength is shifted to the long wavelength side (for example, above 685 nm), which improves the light transmittance of the red region, and the hue of the transmitted light can be closer to the real.

The cubocyanine compound and the ketocyanine compound having a group represented by the formula (14), and the benzene rings on both sides of the ketocyanine skeleton or the ketocyanine skeleton may be connected by a linking group. As such a compound, for example, a squaraine compound disclosed in Japanese Patent Application Laid-Open No. 2015-176046.

From the viewpoint of improving the adhesion when a resin layer is formed on a support (substrate), the resin composition contains at least one selected from a silane coupling agent, a hydrolysis product of a silane coupling agent, and a hydrolysis-condensation product of a silane coupling agent. (Hereinafter, these are collectively referred to as "specific silane compounds.") As the silane coupling agent that can be used here, a silane coupling agent containing an epoxy group, an amine group, or a mercapto group is preferred, and an silane coupling agent containing an epoxy group is particularly preferred. If such a silane coupling agent is used, and the resin composition contains an ethylene compound, 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-containing silane coupling agent may contain only one epoxy group or a plurality of them, and may contain only one alkoxysilyl group or a plurality of them.

When the epoxy group-containing silane coupling agent contains only one alkoxysilane group, as the silane coupling agent, an alkoxysilane having an alkoxy group represented by the following formula (15) is preferably used.

In formula (15), R ⁴¹ represents an epoxy-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. Integer, when k is 2 or more, the plural R ⁴¹ may be the same or different from each other; when m is 2, the plural R ⁴² may be the same or different from each other; when n is 2 or more, the plural OR ⁴³ may be the same Can also be different. R ⁴¹ and R ⁴² and OR ⁴³ and OH are each a group directly bonded to Si.

In the formula (15), the epoxy group-containing group of R ⁴¹ is not particularly limited as long as it contains an epoxy group, but examples thereof include a glycidyl group-containing group and an oxidized cycloolefin (alicyclic formula). Epoxy group) and the like. A glycidyloxy group, a cycloolefin oxide, etc. may be bonded to a silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). R ⁴¹ preferably contains only one epoxy group. Examples of the epoxy group-containing group of R ⁴¹ include glycidoxy, 3-glycidoxypropyl, 8- (glycidoxy) -n-octyl, and 3,4-cyclo Oxycyclohexyl, 2- (3,4-epoxycyclohexyl) ethyl and the like. In addition, from the viewpoint of improving the adhesion of the resin layer to the support, it is preferable that the distance between the epoxy group and the silicon atom contained in R ⁴¹ is not too far, such as propylene oxide, cycloolefin oxide, etc. It is directly bonded to the silicon atom, and preferably bonded to the silicon atom via an alkylene group having 1 to 6 carbon atoms.

In the formula (15), the alkyl groups of R ⁴² and R ⁴³ are preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of R ⁴² include methyl, ethyl, n-propyl, and isopropyl. OR ^{43 is} preferably exemplified by methoxy, ethoxy, n-propoxy, and isopropoxy.

In the formula (15), k is preferably 1 or 2, and 1 is more preferred, thereby making it easy to improve the adhesion of the resin layer to the support. In addition, m is preferably 0 or 1, 0 is more preferable, and n is 2 or 3.

When the epoxy group-containing silane coupling agent includes a plurality of alkoxysilane groups, as the silane coupling agent, a polymer-type polyfunctional epoxy group-containing silane coupling agent (hereinafter, simply referred to as "polymer Type silane coupling agent "). The polymer-type silane coupling agent has a structure in which an epoxy group-containing group and an alkoxysilyl group-containing group are bonded to an organic polymer chain. One molecule includes a plurality of alkoxysilyl groups, and may also include a plurality of epoxy groups. The organic chain of the polymer-type silane coupling agent does not include polysiloxane. Since the polymer-type silane coupling agent can have a plurality of alkoxysilyl groups and epoxy groups in one molecule as described above, it can form a large number of reaction sites with resins and supports, which can improve the density of the resin layer to the supports. Attached.

The hydrolysis product of the epoxy group-containing silane coupling agent can be obtained by hydrolyzing and converting the alkoxysilane group contained in the silane coupling agent into a silanol group. In addition, a hydrolyzed condensate of an epoxy-containing silane coupling agent can be synthesized by dehydrating a silanol group contained in a hydrolysate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). obtain. In general, when a silane coupling agent is hydrolyzed, a hydrolyzed product of the silane coupling agent can be obtained, and a dehydration condensation reaction of a silanol group contained in the hydrolyzed product can be obtained, and a hydrolyzed condensate of the silane coupling agent can be easily obtained. The hydrolyzed condensate of the silane coupling agent may be a dehydrated condensate of a hydrolysis product of the same silane coupling agent, or may be a dehydrated condensate of a hydrolysis product of a different silane coupling agent.

From the viewpoint of improving the adhesion of the resin layer to the support, the resin composition is preferably a hydrolysate or a hydrolysate condensate containing at least an epoxy group-containing silane coupling agent. The resin composition preferably contains a hydrolysate or a hydrolyzed condensate of an alkoxysilane having an epoxy group (for example, an alkoxysilane represented by the above formula (15)), and more preferably contains an alkoxy group having an epoxy group. A hydrolyzed condensate of an alkylsilane (for example, an alkoxysilane represented by the formula (15)). As the dehydrated condensate at this time, for example, when measuring the weight-average molecular weight of the specific silane compound contained in the resin composition, it is preferable that the molecular weight is equal to or less than the molecular weight of the pentamer (but all alkoxy groups are hydroxyl groups). It is preferable that the molecular weight is equal to or lower than the molecular weight of the tetramer. As a specific value of this weight average molecular weight, for example, 300 or more is preferable, 1,000 or less is preferable, 800 or less is more preferable, and 600 or less is more preferable. In addition, the total content of the hydrolysate and hydrolysis condensate of the epoxy group-containing silane coupling agent in 100% by mass of the characteristic silane compound is preferably 10% by mass or more, 30% by mass or more is preferred, and 50% by mass or more is more preferred. good.

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, more preferably 1% by mass or more, and 20% by mass of the solid content of the resin composition. The content is preferably not more than 10% by mass, more preferably not more than 10% by mass, and more preferably not more than 5% by mass.

The content of the specific silane compound in the resin composition can be determined by a gas chromatography method, a high performance liquid chromatography method, or the like. The specific silane compound contained in the resin composition is quantified by various types by gas chromatography, high-performance liquid chromatography, and the like, and the content of the specific silane compound can be determined from the sum thereof. In the case of a dehydrated composition (oligomer such as dimer, trimer, etc.) containing a silane coupling agent, gel permeation chromatography analysis and the like can be used to determine the existence form of the dehydrated composition. For example, when an epoxy group-containing silane coupling agent is hydrolyzed or further dehydrated for synthesis, the amount of the silane coupling agent used in the initial stage is deducted from its residual amount after hydrolyzing or further dehydrating to obtain its hydrolysate. And the content of hydrolysis condensate.

The resin composition may be one containing a solvent. For example, when the resin composition is a paint-formed resin composition, application of the resin composition is facilitated by including a solvent. The coated resin composition can be obtained, for example, by dissolving an ethylene compound and a resin component in a solvent, or by dispersing an ethylene compound and a resin component in a solvent (dispersion medium). The solvent may be a function as a solvent (solvent) of the ethylene compound, or a function as a dispersion medium. Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; PGMEA (2-ethoxyl-1-methoxypropane), ethylene glycol monobutyl ether, and ethyl acetate Ethylene glycol derivatives such as glycol monoethyl ether and ethylene glycol ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); N, N-dimethylacetamide, and other amines; ethyl acetate , Propyl acetate, butyl acetate, and other esters; N-methyl-pyrrolidone (specifically, 1-methyl-2-pyrrolidone and the like) and other pyrrolidones; and aromatics such as toluene and xylene Hydrocarbons; 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. These solvents may be used alone or in combination of two or more.

The content of the solvent is, for example, 100% by mass of the resin composition, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 100% by mass, or 95% by mass or less. By adjusting the content of the solvent within these ranges, a resin composition having a high ethylene compound concentration can be easily obtained.

The resin composition may also contain a surface conditioner. In this way, when the resin composition is cured to form a resin layer, appearance defects such as scratches and depressions on the resin layer can be suppressed. The type of the surface modifier is not particularly limited, but 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, a BYK (registered trademark) series manufactured by BYK-Chemie, a KF series manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like can be used.

The resin composition may also contain a dispersant. In this way, the dispersibility of the ethylene compound and the like in the resin composition is stabilized, and re-aggregation can be suppressed. The type of dispersant is not particularly limited, but EFKA series manufactured by EFKA Additives, BYK (registered trademark) series manufactured by BYK-Chemie, Solsperse (registered trademark) series manufactured by Lubrizol, Japan, and Nanbon Chemical Co., Ltd. can be used. DISPARLON (registered trademark) series, AJISPER (registered trademark) series manufactured by Ajinomoto Fine-Techno, KP series manufactured by Shin-Etsu Chemical Industry Co., Ltd., POLYFLOW series manufactured by Kyoeisha Chemical Co., Ltd., and MEGAFAC (registered trademark) series manufactured by DIC , Sannopco's DISPERSANT series and so on.

The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity adjuster, a defoamer, a preservative, a specific resistance adjuster, and an adhesion improver, if necessary.

A resin composition can be hardened | cured by hardening. The resin composition may be hardened by a reaction of a resin component (for example, a polymerization reaction, a cross-linking reaction, or the like), or may be hardened by drying or removing a solvent contained in the resin composition by heating. As such a resin composition, for example, a thermoplastic resin composition that can be molded by injection molding, extrusion molding, etc., a spin coating method, a solvent casting method, a roll coating method, a spray coating method, Coating resin composition coated by a bar coating method, a dip coating method, a screen printing method, a flexographic printing method, an inkjet method, a slit coating method, or the like. In addition, in the present invention, "hardened" means a state in which the fluidity of the resin composition is reduced, and the fluidity is not substantially maintained. The "hardening" includes a case where the resin composition is cured by a reaction of the resin (for example, a polymerization reaction, a crosslinking reaction, etc.), a case where the solvent contained in the resin composition is removed, and the resin composition is cured.

When the resin composition is a thermoplastic resin composition, the resin composition can be hardened by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this method, a thermoplastic resin is used as a resin component, an ethylene compound is blended in the thermoplastic resin, and a molded product can be obtained by heat molding. For example, an ethylene compound is added to the powder or granules of the base resin, and the resin is heated to about 150 ° C to 350 ° C to dissolve it and then molded. The shape of the molded product is not limited, but examples thereof include a plate shape, a sheet shape, a granular shape, a powder shape, a block shape, a particle aggregate shape, a spherical shape, an elliptical shape, a lens shape, a cube shape, a column shape, and a rod. Shape, cone shape, tube shape, needle shape, fiber shape, hollow filament shape, porous shape, etc. In addition, when the resin is kneaded, additives such as a plasticizer that are generally used in resin molding may be added.

When the resin composition is a coating resin composition, a liquid or paste-like resin composition containing an ethylene compound and a resin component is applied to a substrate (such as a resin plate, a film, a glass plate, etc.), A hardened product such as a film shape having a thickness of 200 μm or less and a sheet shape exceeding 200 μm in thickness can be obtained. The hardened | cured material obtained in this way can be operated as a film, a sheet | seat, etc. by peeling from a base material, and can also be operated as a whole with a base material.

The cured product of the resin composition may be composed of a single resin layer (a layer formed by curing the resin composition), or may be composed of a plurality of resin layers. When the hardened body and the base material are operated in an integrated manner, the hardened body may be formed on only one side of the base material, or may be formed on both sides. In addition, a person who integrates the cured product and the substrate may form a molded body and a substrate formed of the resin composition by thermal bonding and chemically bonding them.

Since the ethylene compound of the present invention is excellent in heat resistance, it can be suitably used in a thermoplastic resin, and when it is thermoformed, heat-pressed, and integrated with a support by chemical bonding, etc., the ultraviolet absorbing effect can be appropriately exhibited. In addition, a resin necessary for a thermosetting reaction at a high temperature (for example, a polyurethane precursor, an epoxy resin, an acrylic resin, etc.) and a resin necessary for drying at a high temperature (for example, a resin containing a high boiling point solvent, glass, etc.) are used. When molding with a resin having a high transition temperature, etc.), due to the excellent heat resistance of the ethylene compound, the ultraviolet absorption effect can be appropriately exhibited.

The ultraviolet absorber, resin composition, and hardened product containing the ethylene compound of the present invention can be used for protecting glass, resin glass, building materials such as interior and exterior materials, coatings, adhesives, automobile components, for placing food, pharmaceuticals, Containers for cosmetics, chemicals, etc., various films (protective film, optical film, phase difference film, packaging film, agricultural film, etc.), various lenses (sunglasses, goggles, blue-ray removing glasses, medical protective glasses, etc. ), Telephone cable sheath materials used for electric wires, etc., members for irradiation devices using ultraviolet as a light source, fibers, display members, touch panels, optical filter members, optical sensor members, surface glass, surface Surface protection members such as panels, filter members to remove harmful light to the human body, various sensor members (including prevention of malfunction), lighting members, solar cell members, kanbans, signs, etc.

The resin composition of the present invention can be used as a resin composition for forming a filter that can be used in various applications such as optical device applications, display device applications, mechanical components, electrical and electronic components, and the like. The resin composition can be suitably used for an optical filter such as an ultraviolet filter, a light selective transmission filter that preferentially transmits light in the visible light region, and the like.

In imaging devices such as mobile phone cameras, digital cameras, in-vehicle cameras, video cameras, and display elements (LEDs), the imaging element that converts the light of the subject into a telecommunication signal is usually used, but this type of imaging The device includes light-receiving devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal-Oxide Semiconductor, etc.), and lenses. It also has high-performance components to remove optical noise (such as ghost images, Light spot, etc.) is selected to pass through the filter. In this type of light selective transmission filter, usually, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated is provided. The dielectric multilayer film is adjusted by adjusting the high refractive index material layer and the low The thickness of each layer of the refractive index material layer can intercept the incidence of light in a predetermined wavelength region.

However, the dielectric multilayer film changes the cutoff wavelength region or the transmission wavelength region due to the angle of incidence. When the angle of incidence changes from a vertical direction to an oblique direction, the cutoff wavelength region, the transmission wavelength region, and the like are shifted to the short wavelength side. Therefore, for the incident light in the oblique direction, the dielectric multilayer film cannot sufficiently intercept light in a preset wavelength region, or light in a visible light region is also intercepted, and a hue change occurs. In particular, in recent years, image pickup elements have been strongly required to be miniaturized and thinned. As the distance between the lens and the light receiving element is shortened, the light receiving element must receive light from an incident light in a more oblique direction. At this time, the incident angle dependence of the cut-off wavelength region and the transmission wavelength region becomes stronger, and the short-wavelength light shift in the short-wavelength region, which has almost no influence in the past, is changed in the ultraviolet to purple region. To be significant.

The resin composition of the present invention contains the ethylene compound as described above. Since the ethylene compound shows a steep absorption peak in the ultraviolet to purple region, the optical filter formed by the resin composition can selectively absorb the ultraviolet to purple region. Light, it can reduce the incident angle dependence of the short wavelength side in the visible light region. In addition, if the resin composition contains an ethylene compound and a near-infrared absorbing dye, the optical filter formed from the resin composition can reduce the incident angle dependency on both the short-wavelength side and the long-wavelength side in the visible light region. In addition, since the vinyl compound contained in the optical filter is excellent in heat resistance, the resin composition can be suppressed from being decomposed when the resin composition is subjected to thermoforming or thermosetting, and a dielectric multilayer film is formed by vapor deposition. Volatilization, etc., can effectively intercept light in the ultraviolet to purple region. Furthermore, when the optical filter is stored, manufactured, processed, or the like (e.g., vapor deposition, mounting, etc.), even if it is exposed to ultraviolet light, degradation of the resin component, near-infrared absorbing pigment, and the like 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. The filter integrated with the support can be formed by, for example, a spin coating method on the surface of the support (or when there is another layer such as an adhesive layer between the support and the resin layer on the surface of the other layer). It is formed by coating a resin composition such as a solvent casting method and drying or hardening it. In addition, a filter may be formed by pressing a planar shaped body formed of a resin composition on a support by hot pressing.

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 ensuring the desired near-infrared cutoff performance, for example, it is preferably 0.5 μm or more, more preferably 1 μm or more, more preferably 2 μm or more, and 1 mm or less. Preferably, 500 μm or less is preferred, and 200 μm or less is more preferred. When a resin layer is formed by applying a coating resin composition or the like to a support, the strength of the filter can be ensured by the support, so that the thickness of the resin layer can be made thinner. The thickness of the resin layer when the resin layer is formed on the support is, for example, preferably 50 μm or less, more preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

As the support, a transparent substrate such as a resin plate, a resin film, or a glass plate is preferably used. The resin plate or resin film which can be used for a support body, For example, it is preferable to use the thing formed from the resin component demonstrated above. From the viewpoint of improving the heat resistance of the optical filter, it is preferable to use a glass substrate as a support. The optical filter thus formed can be mounted on an electronic component by solder reflow, for example. In addition, even if the glass substrate is exposed to high temperatures, cracks, warpage, and the like are unlikely to occur, and adhesion to the resin layer is easily secured. When a glass substrate is used as a support, an adhesive layer formed of, for example, a silane coupling agent may be provided between the support and the resin layer, thereby improving the adhesion between the resin layer and the glass substrate.

Examples of the thickness of the support (substrate) are preferably 0.05 mm or more and 0.1 mm or more from the viewpoint of securing strength, and 0.4 mm or less and 0.3 mm or less from the viewpoint of thinning. good.

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

The optical filter may have a layer (anti-reflection film) that reduces glare, antiglare, and the like of a fluorescent lamp, a layer having anti-scratch performance, a transparent substrate having other functions, and the like. The optical filter may have an ultraviolet reflection film, a near-infrared reflection film, and the like on the resin layer. It is preferable that the ultraviolet reflection film, the near-infrared reflection film, and the like are provided closer to the light incident side than the resin layer. If the optical filter is provided with an ultraviolet reflective film, a near-infrared reflective film, etc., it is possible to intercept ultraviolet, near-infrared, etc. from the transmitted light of the optical filter. The ultraviolet reflection film and the near-infrared reflection film may be those having both the ultraviolet reflection function and the near-infrared reflection function in one sheet.

The ultraviolet reflection film, near-infrared reflection film, and antireflection film (visible light antireflection film) may be composed of a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated. Therefore, when these functions are imparted to the optical filter, it is preferable that the optical filter has a dielectric multilayer film. As a material constituting the high-refractive-index material layer, a material having a refractive index of 1.7 or more can be used. Generally, a material having a refractive index ranging from 1.7 to 2.5 is selected. Examples of the material constituting the high refractive index material layer include titanium oxide, zinc oxide, zirconia, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; silicon nitride, and the like Nitrides; the above-mentioned oxides, mixtures of the above-mentioned nitrides, etc., doped with metals such as aluminum, copper, and carbon (such as tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO) )Wait. 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 ranging from 1.2 to 1.6 is usually selected. Examples of the material constituting the low-refractive-index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The optical filter may further include a film such as an aluminum vapor-deposited film, a precious metal, a resin film containing indium oxide as a main component and dispersing metal oxide fine particles containing a small amount of tin oxide, and the like.

The thickness of the optical filter is preferably, for example, 1 mm or less. In this way, it is possible to sufficiently respond to, for example, a request for miniaturization of an image sensor. The thickness of the optical filter is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 150 μm or less, still more preferably 30 μm or more, and more preferably 50 μm or more.

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

This application claims the right of priority based on Japanese Patent Application No. 2017-132977 filed on July 6, 2017. The entire contents of the Japanese Patent Application No. 2017-132977 filed on July 6, 2017 are incorporated in this application for reference. (Example)

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to the following examples, and can be appropriately modified and implemented within a range that meets the gist described before and after. These are also included in the present invention. Within the scope of technology.

(1) Synthesis of compound (1-1) Synthesis Example 1: Synthesis of ethylene compound 1 In a 200 mL 4-necked flask, 4-fluorobenzaldehyde 4.98 g (0.039 mol) and bis (2-mercaptoethyl) were poured. Ether 2.72 g (0.020 mol), potassium carbonate 10.86 g (0.079 mol), and acetonitrile 74 g were allowed to react at 60 ° C. for 12 hours while stirring with a stirring blade under a nitrogen flow (10 mL / minute). After completion of the reaction, the insoluble component was filtered off under reduced pressure, and then the solvent was distilled off using an evaporator. The obtained concentrate was poured into a 200 mL 4-necked 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, and reacted under reflux for 4 hours. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 6.2 g of an ethylene compound 1. The yield with respect to 4-fluorobenzaldehyde was 71.3 mol%. About 5 mg of the obtained compound was divided and diluted in a predetermined amount of a deuterated solvent (deuterated chloroform or deuterated dimethylsulfinium), and the structure was determined by ¹ H-NMR measurement.

[Chemical 11] Ethylene compound 1

(1-2) Synthesis Example 2: Synthesis of Ethylene Compound 2 Except that methyl cyanoacetate was used in place of malononitrile in Synthesis Example 1, the same procedures as in Synthesis Example 1 were used to obtain the ethylene compound 2 shown in Table 1. 15.9 g. The yield with respect to 4-fluorobenzaldehyde was 87.4 mol%.

(1-3) Synthesis Example 3: Synthesis of Ethylene Compound 3 An ethylene compound shown in Table 1 was obtained in the same procedure as in Synthesis Example 1, except that dimethyl malonate was used in place of malononitrile in Synthesis Example 1. 3 has 3.4 g. The yield relative to 4-fluorobenzaldehyde was 35.7 mol%.

(1-4) Synthesis Example 4: Synthesis of Ethylene Compound 4 Ethylene compounds shown in Table 1 were obtained in the same procedure as in Synthesis Example 3, except that the same amount of acetic acid as piperidine was added in Synthesis Example 3. 4 has 6.1 g. The yield with respect to 4-fluorobenzaldehyde was 80.0 mol%.

(1-5) Synthesis Example 5: Synthesis of Ethylene Compound 5 Except that butyl cyanoacetate was used instead of malononitrile in Synthesis Example 1, the same procedure as in Synthesis Example 1 was used to obtain the ethylene compound 5 shown in Table 1. 1.3 g. The yield with respect to 4-fluorobenzaldehyde was 14.8 mol%.

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

(1-7) Synthesis Example 7: Synthesis of Ethylene Compound 7 Except that in Synthesis Example 1, 2-ethylhexyl cyanoacetate was used in place of malononitrile, the same procedure as in Synthesis Example 1 was performed to obtain the compounds shown in Table 1. The ethylene compound 7 had 2.5 g. The yield relative to 4-fluorobenzaldehyde was 24.2 mol%.

(1-8) Synthesis Example 8: Synthesis of Ethylene Compound 8 Except for using Michler's acid in place of malononitrile in Synthesis Example 1, the same procedure as in Synthesis Example 1 was used to obtain the ethylene compound 8 shown in Table 1. g. The yield with respect to 4-fluorobenzaldehyde was 49.1 mol%.

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

(1-10) Synthesis Example 10: Synthesis of ethylene compound 10 In addition to Synthesis Example 2, ethylene glycol bis (2-mercaptoethyl) ether was used instead of bis (2-mercaptoethyl) ether. 2 In the same procedure, 3.8 g of the ethylene compound 10 shown in Table 2 was obtained. The yield with respect to 4-fluorobenzaldehyde was 75.6 mol%.

(1-11) Synthesis Example 11: Synthesis of ethylene compound 11 In addition to Synthesis Example 3, ethylene glycol bis (2-mercaptoethyl) ether was used in place of bis (2-mercaptoethyl) ether. 3 In the same order, 1.1 g of the ethylene compound 11 shown in Table 2 was obtained. The yield relative to 4-fluorobenzaldehyde was 25.2 mol%.

(1-12) Synthesis Example 12: Synthesis of ethylene compound 12 In addition to Synthesis Example 6, ethylene glycol bis (2-mercaptoethyl) ether was used in place of bis (2-mercaptoethyl) ether. 6 In the same procedure, 4.6 g of the ethylene compound 12 shown in Table 2 was obtained. The yield relative to 4-fluorobenzaldehyde was 79.6 mol%.

(1-13) Synthesis Example 13: Synthesis of ethylene compound 13 In a 200 mL 4-necked flask, 4.61 g (0.0328 mol) of 4-chlorobenzaldehyde, and ethylene glycol bis (2-mercaptoethyl) ether 2.92 were poured. g (0.016 mol), potassium carbonate 6.63 g (0.048 mol), tetrabutylammonium bromide 0.52 g (0.0016 mol), acetonitrile 30.11 g, under nitrogen flow (10 mL / min), use a stirring blade while stirring at 75 The reaction was allowed to proceed at 6 ° C for 6 hours. After completion of the reaction, the insoluble component was filtered off under reduced pressure, and then the solvent was distilled off using an evaporator. The obtained concentrate was poured into a 200 mL 4-necked flask, 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, and reacted under reflux for 2 hours. . After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 7.0 g of the ethylene compound 13 shown in Table 2. The yield with respect to 4-chlorobenzaldehyde was 92.0 mol%. About 5 mg of the obtained compound was divided and diluted in a predetermined amount of a deuterated solvent (deuterated chloroform or deuterated dimethylsulfinium), and the structure was determined by ¹ H-NMR measurement.

(1-14) Synthesis Example 14: Synthesis of Ethylene Compound 14 In a 200 mL 4-neck flask, the ethylene compound 13 obtained in Synthesis Example 13 was poured into 4.75 g (0.010 mol) and 0.19 g of p-toluenesulfonic acid monohydrate. (0.001 mol) and 80 g of 1-butanol under a nitrogen flow (10 mL / minute), the reaction was allowed to proceed for 5 hours under reflux while stirring using a stirring blade. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 4.9 g of the ethylene compound 14 shown in Table 2. The yield with respect to 4-chlorobenzaldehyde was 83.5 mol%. About 5 mg of the obtained compound was divided and diluted in a predetermined amount of a deuterated solvent (deuterated chloroform or deuterated dimethylsulfinium), and the structure was determined by ¹ H-NMR measurement.

(1-15) Synthesis Example 15: Comparative synthesis of ethylene compound 1 In a 200 mL 4-necked flask, pour 4-fluorobenzaldehyde 3.85 g (0.031 mol) and 4-chlorobenzyl mercaptan 5.02 g (0.031 mol) ), 8.57 g (0.062 mol) of potassium carbonate, and 36 g of acetonitrile, and reacted at 60 ° C. for 12 hours with stirring using a stirring blade under a nitrogen flow (10 mL / min). After completion of the reaction, the insoluble component was filtered off under reduced pressure, and then the solvent was distilled off using an evaporator. The obtained concentrate was poured into a 200 mL 4-necked 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, and reacted under reflux for 4 hours. . After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain 8.9 g of the comparative ethylene compound 1 shown in Table 2. The yield relative to 4-fluorobenzaldehyde was 92.6 mol%.

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

(1-17) Synthesis Example 17: Synthesis of Comparative Ethylene Compound 3 A table was obtained in the same order as in Synthesis Example 15 except that 4-isopropylthiophenol was used instead of 4-chlorobenzyl mercaptan in Synthesis Example 15. Comparative ethylene compound 3 shown in 2 had 3.5 g. The yield with respect to 4-fluorobenzaldehyde was 71.9 mol%.

[Table 1

[Table 2]

(2) Preparation of epoxy resin (EP resin) composition (2-1) Preparation of hardening catalyst According to the synthesis method described in International Publication No. 1997/031924, TPB (tris (pentafluorophenyl)) is prepared. 255 g of Isopar (registered trademark) E solution made by ANDOH PARACHEMIE company with a content of 7%. Water was dropped into the solution at 60 ° C to precipitate white crystals. After cooling to room temperature, the solution was suction-filtered and washed with n-heptane. The obtained filter cake was dried under reduced pressure at 60 ° C to obtain 18.7 g of a TPB · water complex (containing TPB powder) as white crystals. This compound has a moisture content of 9.2% (Khash Moisture Analyzer) and a TPB content of 90.8%. ¹⁹ F-NMR analysis and GC analysis were performed on the dried composite, but no peak other than TPB was measured. 2.0 g of the obtained TPB‧water complex was mixed with 1.1 g of toluene, and mixed at room temperature for 10 minutes. Thereafter, 2.6 g of a 2 mol / L aqueous ammonia-ethanol solution was added and mixed at room temperature for 60 minutes to obtain a homogeneous solution of the TPB catalyst. These are used as cation hardening catalysts.

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

(2-3) Preparation of epoxy resin composition 1 1,2-epoxy-4- (2-, 2-bis (hydroxymethyl) -1-butanol as epoxy resin 100 parts by mass of an ethylene oxide group) cyclohexane adduct (manufactured by Daicel, EHPE3150), 150 parts by mass of toluene as a solvent, and 75 parts by mass of o-xylene, and the following formula as a near-infrared absorbing pigment 8.9 parts by mass of acid cyanine compound A (described in Examples 1-18 of Japanese Patent Application Laid-Open No. 2016-74649), 8.4 parts by mass of ethylene compound 2 obtained in Synthesis Example 2, BYK manufactured by BYK-Chemie as a surface conditioner -306 (polyether modified polydimethylsiloxane) was formulated in 0.3 parts by mass, and uniformly mixed at 40 ° C. After the resulting mixture was cooled to 25 ° C., 2.5 parts by mass of the cation hardening catalyst obtained above and 10 parts by mass of the silane hydrolysate solution were added and uniformly mixed. These were filtered through a 0.45 μm filter membrane (manufactured by GL Sciences, non Aqueous system 13N) filtered to remove foreign matter to obtain epoxy resin composition 1.

[Chemical 12] Squarine compound A

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

(2-5) Preparation of epoxy resin composition 3 An epoxy resin composition was obtained in the same procedure except that the comparative ethylene compound 1 was used instead of the ethylene compound 2 in the preparation example of the epoxy resin composition 1 described above. 3.

(2-6) Preparation of epoxy resin composition 4 An epoxy resin composition was obtained in the same procedure except that the comparative ethylene compound 2 was used instead of the ethylene compound 2 in the preparation example of the epoxy resin composition 1 described above. 4.

(2-7) Preparation of epoxy resin composition 5 An epoxy resin composition was obtained in the same procedure except that the comparative ethylene compound 3 was used instead of the ethylene compound 2 in the preparation example of the epoxy resin composition 1 described above. 5.

(3) Preparation of cycloolefin-based resin (COP resin) composition (3-1) Preparation of cycloolefin-based resin composition 1 Cycloolefin-based resin (manufactured by POLYPLASTICS, TOPAS (registered trademark) 5013) 126 parts by mass In a mixed solvent of 435 parts by mass of toluene and 439 parts by mass of o-xylene, 10 parts by mass of the above-mentioned squaryl cyanine compound A was added, and 8.4 parts by mass of the ethylene compound 1 obtained in Synthesis Example 1 was used as a surface modifier. 0.52 parts by mass of BYK-330 (polyether modified polydimethylsiloxane) manufactured by BYK-Chemie Co., Ltd. was uniformly mixed to obtain a cycloolefin-based resin composition 1.

(3-2) Preparation of Cycloolefin-based Resin Composition 2 A cycloolefin-based resin composition was obtained in the same procedure except that, in the preparation example of the cycloolefin-based resin composition 1, the comparative ethylene compound 1 was used instead of the ethylene compound 1. 2.

(3-3) Preparation of cycloolefin-based resin composition 3 A cycloolefin-based resin composition was obtained in the same procedure except that in the above-mentioned preparation example of the cycloolefin-based resin composition 1, the comparative ethylene compound 3 was used instead of the ethylene compound 1. 3.

(4) Preparation of polyarylate resin (PAR resin) composition (4-1) Synthesis of polyarylate resin In a reaction vessel with a capacity of 2 liters equipped with a stirring blade, pour 2,2'-double (4 -Hydroxyphenyl) propane 10.01 g (0.044 mol), sodium hydroxide 3.59 g (0.090 mol), and 300 g of ion-exchanged water were dissolved, and then 0.89 g (0.009 mol) of triethylamine was added to dissolve them. A solution of 3.57 g (0.021 mol) of terephthalocyanine and 3.57 g (0.021 mol) of isophthalocyanine in 500 g of methylene chloride was poured into a dropping funnel, and these were installed in the above reaction container. . The solution in the reaction vessel was maintained at 20 ° C while stirring, and the methylene chloride solution was dropped from the dropping funnel over a period of 60 minutes. Furthermore, a solution in which 0.71 g (0.005 mol) of benzamidine chloride was dissolved in 10 g of methylene chloride was added, and stirred for 60 minutes. An acetic acid aqueous solution was added to the obtained reaction solution for neutralization. When the pH of the aqueous phase reached 7, the oil phase and the aqueous phase were separated using a separatory funnel. The obtained oil phase was dropped into methanol to re-precipitate the polymer under stirring, and Shen Dianwu was recovered by filtration and oven-dried 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 calculated for polystyrene by gel permeation chromatography.

(4-2) Preparation of Polyarylate 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 it was added as near infrared rays. BYK-Chemie has 3.3 parts by mass of the cyanocyanine compound A that absorbs the pigment, 1.1 parts by mass of the cyanocyanine compound B shown below, and 8 parts by mass of the ethylene compound 12 obtained in Synthesis Example 12. 0.52 parts by mass of BYK-330 (polyether modified polydimethylsiloxane) manufactured by the company was uniformly mixed to obtain polyarylate resin composition 1.

[Chemical 13] Squarine compound B

(4-3) Preparation of polyarylate 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 the above-mentioned method was added thereto. The acid cyanine compound A had 3.3 parts by mass, and the comparative ethylene compound 1 obtained in Synthesis Example 13 had 8.4 parts by mass. BYK-330 (polyether modified polydimethylsiloxane) manufactured by BYK-Chemie Co., Ltd. as a surface conditioner 0.52 The parts by mass were uniformly mixed to obtain a polyarylate resin composition 2.

(4-4) Preparation of polyarylate resin composition 3 The polyarylate resin composition 1 obtained above and the hydrolysis solution of the epoxy group-containing silane coupling agent were the former: the latter having a mass ratio of 99: 1 to 25. The mixture was uniformly mixed at a temperature of 0 ° C., and these were filtered through a filter membrane (manufactured by GL SCIENCES, non-aqueous 13N) having a pore size of 0.1 μm to remove foreign matter, thereby obtaining a polyarylate resin composition 3. The hydrolysis solution of the epoxy group-containing silane coupling agent was prepared by adding 24.7 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., OFS-6040) and 2-propanol 32.1 The mass parts and 3.4 mass parts of distilled water were prepared, and after uniformly mixing at 25 ° C, 1.54 parts by mass of formic acid was added and mixed for 90 minutes to prepare a hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane.

(4-5) Preparation of Polyarylate Resin Composition 4 In addition to the above-mentioned preparation example of the polyarylate resin composition 3, a squaraine compound C (Tetrahedron Letters, Vol. .40, pp. 4067-4068 (1999) Table 3 Product 3a) Substituting squarocyanine compound A and squarocyanine compound B, and using ethylene compound 14 obtained in Synthesis Example 14 instead of ethylene compound 12, A polyarylate resin composition 4 was obtained in the same procedure as in the preparation example of the polyarylate resin composition 3.

[Chemical 14] Squarine compound C

(4-6) Preparation of Polyarylate Resin Composition 5 A polyarylate was obtained in the same order except that the polyarylate resin composition 3 was prepared without using the squaraine compound A and the squaraine compound B. Resin composition 5.

(4-7) Preparation of polyarylate resin composition 6 In addition to the preparation example of polyarylate resin composition 5, 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray, OFS) was used. -6040) 24.7 parts by mass and 32.1 parts by mass of 2-propanol and 3.4 parts by mass of distilled water and 1.54 parts by mass of formic acid were used in place of the hydrolysis solution of the epoxy-containing silane coupling agent, and a polyarylate resin was obtained in the same order. Composition 6.

(4-8) Preparation of polyarylate resin composition 7 A polyarylate resin composition 7 was obtained in the same procedure, except that the squaryl cyanine compound C was not used in the preparation example of the polyarylate resin composition 4.

(4-9) Preparation of polyarylate resin composition 8 A polyarylate resin composition 8 was obtained in the same procedure except that the polyarylate resin composition 3 was prepared without using the ethylene compound 12.

(5) Production of optical filter After dropping 2cc of each of the resin compositions obtained above on a glass substrate (Schott Corporation, D263Teco), a spin coater (MIKASA Corporation, 1H-D7) was used, which took 0.2 seconds. After reaching 1600 rotations, the number of rotations was maintained for 20 seconds, and then it took 0.2 seconds to return to 0 times, and the resin composition was formed on a glass substrate. The glass substrate on which the resin composition was formed was subjected to initial drying (before curing) at 100 ° C for 3 minutes using a precision thermostat (manufactured by Yamato Scientific, DH611). Then, after using a non-oxidation oven (Yamato Scientific, DN6101) at 50 ° C for 30 minutes under nitrogen, the temperature was raised to 190 ° C in about 15 minutes, and drying was performed at 190 ° C for 30 minutes under a nitrogen atmosphere. A resin layer (absorptive layer) was formed thereon (after curing). The thickness of the resin layer formed on the glass substrate was 2 μm. An optical filter is produced by forming a resin layer on a glass substrate in this manner. The thickness of the resin layer is determined by measuring the thickness of the glass substrate on which the resin layer is formed and the thickness of the glass substrate alone with a micrometer, and can be determined from the difference between the two.

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

[table 3]

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

(6-3) Results As shown in Fig. 1, each of the absorption spectra in toluene of ethylene compound 1 and comparative ethylene compound 1 showed a maximum absorption peak at a wavelength of about 380 nm. The transmission spectrum of an optical filter formed of a resin composition containing an ethylene compound or a squaraine compound is shown in Figs. 2, 3, 7, 7, 10, and 12. No significant change was seen before and after curing at 190 ° C. On the other hand, the transmission spectrum of an optical filter formed of a resin composition containing a comparative ethylene compound and a squaraine compound is shown in FIGS. 4 to 6, 8, 9, and 11 The transmittance in the ultraviolet-violet region after curing at 190 ° C becomes higher. From these results, it can be seen that the vinyl compound of the present invention has a good heat resistance.

(7) Evaluation of adhesion (7-1) Initial peel resistance test The resin layer of the optical filter obtained as described above was cut with a cutter (manufactured by NT Corporation, A-300), and the results were measured in a row and a row respectively. Eighty square lines were set at 2 mm intervals to make 81 4 mm ² squares, and a sample substrate for evaluation was produced. This sample substrate was affixed with an adhesive tape (3M company, Scotch (registered trademark) transparent adhesive tape transparent beauty (registered trademark)) without air ingress, and left for 5 seconds. Thereafter, the tape was peeled off from the sample substrate within 1 second, and evaluated based on the following criteria. In addition, the peeling of the tape is performed so that the peeling force is constant for each piece. A: Among the 81 squares produced, no peeling occurred even in one piece B: Among the 81 squares produced, peeling occurred in 1 to 9 blocks C: Among the 81 squares produced, 10 to 81 blocks Flaking

(7-2) Peeling resistance test after boiling in water The resin layer of the optical filter obtained above was cut with a cutter (manufactured by NT Corporation, A-300), and was set at 2 mm intervals in the in-line and the horizontal rows, respectively. Eighty square lines were used to make 81 4 mm ² squares, and sample substrates for evaluation were produced. Next, this sample substrate was put into ultrapure water heated to a boiling state and boiled for 2 hours. Next, at room temperature, an adhesive tape (Scotch (registered trademark) transparent adhesive tape, transparent beauty (registered trademark), manufactured by 3M Co., Ltd.) was prevented from entering, and left for 5 seconds. Thereafter, the tape was peeled off from the sample substrate within 1 second, and evaluated based on the following criteria. In addition, the peeling of the adhesive tape is performed so that the peeling force is fixed for each piece. A: One of the 81 squares produced did not peel off. B: Of the 81 squares produced, peeling occurred from 1 to 9. C: Of the 811 squares produced, 10 to 81. Flaking

[Table 4]

(7-3) Results Table 4 shows the results of the initial peel resistance test and the peel resistance test after optical boiling of the optical filters produced using the polyarylate resin compositions 1, 3 to 8. It is clear from the results in Table 4 that the optical filter-based resin layer formed of the resin composition containing the ethylene compound of the present invention and the silane coupling agent or its hydrolyzed (condensed) product has good adhesion to the glass substrate. . (Industrial availability)

The ethylene compound of the present invention is formulated into a resin to be formed into a film, etc., and can be used for optical selective transmission filters and the like useful in applications such as optical devices, display devices, mechanical components, and electrical-electronic components.

no.

[FIG. 1] It is an absorption spectrum in toluene of ethylene compound 1 and comparative ethylene compound 1 obtained in the example. [Figure 2] 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 the example. 3 is a transmission spectrum of an optical filter formed of an epoxy resin composition 2 containing an ethylene compound 14 obtained in an example. 4 is a transmission spectrum of an optical filter formed of an epoxy resin composition 3 containing a comparative ethylene compound 1 and a near-infrared absorbing dye obtained in an example. [FIG. 5] 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 an example. 6 is a transmission spectrum of an optical filter formed of an epoxy resin composition 5 containing a comparative ethylene compound 3 and a near-infrared absorbing dye obtained in an example. 7 is a transmission spectrum of an optical filter formed of a cycloolefin-based resin composition 1 containing the ethylene compound 1 and a near-infrared absorbing dye obtained in the example. [Figure 8] A transmission spectrum of an optical filter formed from a cycloolefin-based resin composition 2 containing a comparative ethylene compound 1 and a near-infrared absorbing dye obtained in the example. [Figure 9] A transmission spectrum of an optical filter formed of a cycloolefin-based resin composition 3 containing a comparative ethylene compound 3 and a near-infrared absorbing dye obtained in an example. [Fig. 10] Fig. 10 is a transmission spectrum of an optical filter formed of a polyarylate resin composition 1 containing the ethylene compound 12 and a near-infrared absorbing dye obtained in the example. 11 is 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 the example. 12 is a transmission spectrum of an optical filter formed of the polyarylate resin composition 4 containing the ethylene compound 14 and the near-infrared absorbing dye obtained in the example.

Claims (10)

An ethylene compound characterized by the following formula (1), [Chem. 1] [In formula (1), L represents a linking group of two or more valences, a represents an integer of two or more, and A each independently represents a group represented by the following formula (2)], [Chemical formula 2] [In formula (2), R ¹ represents a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, a fluorenyl amino group, or a halogenated alkyl group, and R ² represents a hydrogen atom, a cyano group, a fluorenyl group, a carboxyl group, a carboxylic acid ester group, Fluorenylamino, hydrocarbon or heteroaryl, when R ¹ and R ^{2 are} both fluorenyl, carboxylate or fluorenyl, R ¹ and R ² may be connected to each other to form a ring, and R ³ represents a hydrogen atom Or 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 as or different from each other, X represents a sulfur atom or an oxygen atom, and * represents a group bonded to the linking group L of formula (1) Parts]. For example, the ethylene compound according to item 1 of the patent application range, wherein the above R ² represents a hydrogen atom, a cyano group, a fluorenyl group, a carboxylate group, or a fluorenyl group. For example, the ethylene compound of the first or second patent application range, wherein the absorption spectrum in the wavelength range of 300 nm to 600 nm measured in toluene has a maximum absorption peak at a wavelength of 420 nm or less. A UV absorber is an ethylene compound containing any one of the first to third patent applications. A resin composition includes an ethylene compound and a resin component according to any one of claims 1 to 3 of the scope of patent application. For example, the resin composition according to item 5 of the patent application scope further includes a near-infrared absorbing pigment and / or a visible light absorbing pigment. For example, the resin composition according to claim 5 or claim 6, further comprising at least one selected from the group consisting of an epoxy group-containing silane coupling agent, a hydrolysis product thereof, and a hydrolysis condensation product thereof. A hardened product is obtained by hardening the resin composition of any one of claims 5 to 7 of the scope of patent application. An optical filter includes a resin composition according to any one of claims 5 to 7 or a hardened product according to claim 8. The utility model relates to a sensor, which is provided with an optical filter with a patent application scope of item 9.