Ethylene compounds

Abstract

To provide a compound which exhibits an absorption peak in an ultraviolet-violet region and is highly soluble to an organic solvent.SOLUTION: An ethylene compound represented by a formula below is provided. In the formula, L represents an alkylene group, -O-, -S-, -SO-, a methine group (-C<) optionally having an alkyl group, a tetravalent linking group of >C<, or a linking group consisting of a combination of the aforementioned, "a" represents an integer of 2 or more, where each group bonded to L is linked to others through 6 or more atoms, R1 represents an alkyl group, R2 represents a hydrogen atom or an alkyl group, R3 represents a hydrogen atom, an organic group, or a polar functional group, and X represents a sulfur atom or an oxygen atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ethylene compound capable of absorbing light in the ultraviolet to violet region. [Background technology]

[0002] Various compounds that absorb light in the ultraviolet to violet region have been known. As such compounds, for example, Patent Document 1 discloses benzophenone-based compounds, Patent Document 2 discloses merocyanine-based compounds, and Patent Document 3 discloses triazine-based compounds. Furthermore, Patent Documents 4 to 6 disclose resin compositions containing compounds that absorb light in the ultraviolet to violet region, and optical films formed from the resin compositions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-285927 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-100787 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-82707 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-26942 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-43259 [Patent Document 6] Japanese Patent Application Publication No. 2019-14707 Summary of the Invention [Problem to be solved by the invention]

[0004] In a resin composition containing a compound that absorbs light in the ultraviolet to violet region (hereinafter sometimes referred to as "ultraviolet-absorbing compound"), it is desirable that the ultraviolet-absorbing compound be uniformly dissolved in the resin, which facilitates imparting desired spectral characteristics and ultraviolet absorption characteristics to the cured resin. Furthermore, when the ultraviolet-absorbing compound is dissolved in the resin at a high concentration, the desired spectral characteristics and ultraviolet absorption characteristics can be exhibited even when the resin is molded into a thin film, making it suitable for use in display devices that require thinness, such as liquid crystal displays and organic electroluminescence (EL) displays. In this case, if the ultraviolet-absorbing compound has excellent solubility in the resin, this reduces the likelihood of turbidity in the cured resin or bleeding out of the ultraviolet-absorbing compound in the cured resin, which is preferable. When preparing such a resin composition, it is desirable to be able to handle the ultraviolet-absorbing compound by dissolving it in an organic solvent at a high concentration. By mixing a solution in which the ultraviolet-absorbing compound is dissolved at a high concentration with the resin, a resin composition in which the ultraviolet-absorbing compound is dissolved uniformly and at a high concentration in the resin can be easily obtained.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound that exhibits an absorption peak in the ultraviolet to violet region and has excellent solubility in organic solvents, as well as a resin composition and an optical filter that contain the compound. [Means for solving the problem]

[0006] The present invention includes the following inventions. [1] An ethylene compound represented by the following formula (1): [ka] [In formula (1), L represents an alkylene group, -O-, -S-, -SO-, a methine group (-C<) which may have an alkyl group, a tetravalent linking group of >C<, or a linking group formed by combining these; a represents an integer of 2 or more, Each A independently represents a group represented by the following formula (2): The groups A are linked to each other via a linking group L via six or more atoms. [ka] [In formula (2), R 1 represents a linear alkyl group having 2 or more carbon atoms, a branched alkyl group having 3 or more carbon atoms branched at the α-position carbon, or a branched alkyl group having 5 or more carbon atoms branched at a carbon other than the α-position, R 2 represents a hydrogen atom or an alkyl group, R 3 represents a hydrogen atom, an organic group, or a polar functional group, and multiple R 3 may be the same or different from each other, X represents a sulfur atom or an oxygen atom; * represents the bonding site with the linking group L in formula (1). [2] The ethylene compound according to [1], which has a maximum absorption peak at a wavelength of 340 nm or more and 400 nm or less in an absorption spectrum measured in toluene over a wavelength range of 300 nm to 600 nm. [3] An ultraviolet absorber comprising the ethylene compound according to [1] or [2]. [4] An ethylene compound solution comprising the ethylene compound according to [1] or [2] and a solvent. [5] A resin composition comprising the ethylene compound according to [1] or [2] 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] A cured product obtained by curing the resin composition according to [5] or [6]. [8] An optical filter comprising the resin composition according to [5] or [6]. [9] A sensor comprising the optical filter described in [8]. [Effects of the Invention]

[0007] The ethylene compound of the present invention exhibits an absorption peak in the ultraviolet (UVA) to violet region and has excellent solubility in organic solvents. Since the ethylene compound of the present invention can effectively absorb light, particularly light on the relatively long wavelength side of UVA, when blended with a resin to form a resin composition and an optical filter, the resulting resin composition has a cutoff wavelength range near the boundary between the visible light region and the ultraviolet region, effectively reducing the incidence angle dependency on the short wavelength side of the visible light region. [Brief explanation of the drawings]

[0008] [Figure 1] 1 shows the absorption spectrum of ethylene compound 1 obtained in an example in toluene. [Figure 2] 1 shows the transmission spectrum of an optical filter formed from an epoxy resin composition obtained in an example. [Figure 3] 1 shows the transmission spectrum of an optical filter formed from polyarylate resin composition 1 obtained in an example. [Figure 4] 1 shows the transmission spectrum of an optical filter formed from polyarylate resin composition 2 obtained in Example. DETAILED DESCRIPTION OF THE INVENTION

[0009] The ethylene compound of the present invention is represented by the following formula (1): The ethylene compound represented by the following formula (1) exhibits a sharp absorption peak in the ultraviolet to violet region and can function as an ultraviolet-absorbing ethylene compound.

[0010] [ka]

[0011] In formula (1), L represents an alkylene group, -O-, -S-, -SO-, a methine group (-C<) which may have an alkyl group, a tetravalent linking group of >C<, or a linking group combining these, a represents an integer of 2 or more, and each A independently represents a group represented by the following formula (2), and multiple groups A are linked to each other via the linking group L via 6 or more atoms.

[0012] [ka]

[0013] In formula (2), R 1 represents a linear alkyl group having two or more carbon atoms, a branched alkyl group having three or more carbon atoms branched at the α-position carbon, or a branched alkyl group having five or more carbon atoms branched at a carbon other than the α-position, and R 2 represents a hydrogen atom or an alkyl group, and R 3 represents a hydrogen atom, an organic group, or a polar functional group, and multiple R 3 may be the same or different, X represents a sulfur atom or an oxygen atom, and * represents the bonding site with the linking group L in formula (1).

[0014] In the group A represented by formula (2), the carboxylic acid ester group (-COOR 1 The ethylene structural moiety containing a carboxylic acid ester group and a cyano group (-CN) functions as a chromophore. The ethylene compound represented by formula (1) has group A in which a carboxylic acid ester group and a cyano group are bonded to the ethylene group, and thus can effectively absorb light in the ultraviolet (UVA) to violet region, particularly light on the relatively long wavelength side of UVA, for example, light in the wavelength range of 340 nm to 400 nm. Furthermore, by bonding two or more groups A to the linking group L, the molecular weight of the ethylene compound increases, the boiling point becomes higher, and heat resistance improves. Therefore, for example, even when blended with a resin and subjected to heat molding or heat curing, decomposition of the ethylene compound can be suppressed, and the ethylene compound can be present at a high concentration even in the cured resin product that has undergone heat treatment. Note that in formula (2), -COOR 1 (or -CN) is R 2It may be in the cis position or the trans position relative to the

[0015] In group A, -COOR 1 R 1 represents a linear alkyl group having 2 or more carbon atoms, a branched alkyl group having 3 or more carbon atoms branched at the α-position carbon, or a branched alkyl group having 5 or more carbon atoms branched at a carbon other than the α-position. The ethylene compound represented by formula (1) can be obtained by adding a carboxylic acid ester group, -COOR 1 R 1 By selecting an appropriate alkyl group for the ethylene compound, the ethylene compound will have excellent solubility in organic solvents and resins. Therefore, it becomes easy to incorporate a high concentration of the ethylene compound into the resin composition, and even when forming an ultraviolet absorbing layer from the resin composition, even if the layer is formed to a thin thickness, it can preferably absorb light in the ultraviolet to purple region due to the ethylene compound. The ethylene compound represented by formula (1) also has excellent heat resistance, so that even in a resin cured product that has undergone heat treatment, it can effectively absorb light in the ultraviolet to purple region in accordance with the inherent absorption spectrum of the ethylene compound. Note that, when R of multiple groups A contained in the ethylene compound is 1 may be the same or different from each other.

[0016] R 1 The number of carbon atoms in the linear alkyl group R is not particularly limited as long as it is 2 or more, but from the viewpoint of improving solubility in organic solvents and resins, it is preferably 3 or more, and more preferably 4 or more. 1 The upper limit of the number of carbon atoms in the linear alkyl group is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and may be 6 or less, or 5 or less, from the viewpoint of increasing the absorption coefficient per unit mass of the ethylene compound. 1 By specifying the upper limit of the number of carbon atoms in the linear alkyl group, the production and purification of the ethylene compound becomes easier. 1 Examples of the linear alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group.

[0017] R 1 The branched alkyl group of R includes a branched alkyl group branched at the α-position carbon (i.e., the carbon adjacent to the oxygen atom of -COO-) and a branched alkyl group branched at a carbon other than the α-position. 1 The number of carbon atoms in the branched alkyl group branched at the α-position of R is 3 or more because it is branched. 1 The number of carbon atoms in the branched alkyl branched at a carbon atom other than the α-position of R is 5 or more, preferably 6 or more, and more preferably 7 or more. 1 By specifying the number of carbon atoms in the branched alkyl group, the solubility of the ethylene compound in organic solvents and resins can be increased. 1 The upper limit of the number of carbon atoms in the branched alkyl group R is not particularly limited, but from the viewpoint of increasing the absorption coefficient per unit mass of the ethylene compound, it is preferably 20 or less, more preferably 12 or less, and even more preferably 9 or less. 1 If the branched alkyl group is branched at the α-position carbon, R 1 The number of carbon atoms in the branched alkyl group may be even smaller, for example, 8 or less, 6 or less, or 5 or less. 1 By specifying the upper limit of the number of carbon atoms in the branched alkyl group, the production and purification of the ethylene compound becomes easier. Note that the branched alkyl group branched at the α-position carbon may also be branched at a carbon other than the α-position, but is preferably branched only at the α-position carbon. The branched alkyl group branched at a carbon other than the α-position is preferably branched only at a carbon other than the α-position.

[0018] R 1 Examples of the branched alkyl group branched at the carbon atom at the α-position of R include an isopropyl group, a sec-butyl group, a tert-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 1-methylpentyl group, a 1-ethylbutyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-ethylpropyl group, a 1-methylhexyl group, a 1-ethylpentyl group, a 1,1-dimethylpentyl group, a 1-methyl-1-ethylbutyl group, and a 1,1-diethylpropyl group. 1Examples of branched alkyl groups branched at a carbon atom other than the α-position include 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, and 2,2-dimethylpentyl groups. , 2,3-dimethylpentyl group, 3,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 4,4-dimethylpentyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, and the like.

[0019] R in Equation (2) 2 represents a hydrogen atom or an alkyl group. 2 Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl; and cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Some of the hydrogen atoms in the alkyl group may be substituted with an alkoxy group, an aryl group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or the like. The number of carbon atoms in the alkyl group (excluding the number of carbon atoms in the substituent) is preferably 1 to 20. Specifically, if the alkyl group is a linear or branched group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. If the alkyl group is a cyclic group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8. R 2The alkyl group in R is preferably a linear or branched alkyl group, and preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. 2 A hydrogen atom is particularly preferred as R. 2 may be the same or different from each other.

[0020] In the group A represented by formula (2), the benzene ring bonded to the ethylene structural unit functions to donate electrons to the ethylene structural unit together with X (sulfur atom or oxygen atom) bonded to the benzene ring, and adjusts the absorption wavelength of the chromophore of the ethylene structural unit to be in the ultraviolet to purple region. 3 represents a hydrogen atom, an organic group, or a polar functional group. In the multiple groups A contained in the ethylene compound, R 3 may be the same or different, and multiple R 3 may be the same or different from each other.

[0021] R in Equation (2) 3 Examples of the organic group in R include an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an aryloxycarbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amido group, a sulfonamide group, a carboxy group (a carboxylic acid group), and a cyano group. 3 Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, and a sulfo group (sulfonic acid group).

[0022] R 3 Specific examples of alkyl groups are those listed above for R 2 The description of alkyl groups is given in R. 3 The alkyl group may have a substituent, and examples of the substituent that the alkyl group has include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxyl group, an alkoxyl group, a cyano group, a nitro group, an amino group, and a sulfo group.

[0023] R 3 Specific examples of the alkyl group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group are R 3 Reference is made to the description of alkyl groups in the above.

[0024] R 3 Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and an indenyl group. The aryl group may have a substituent, and examples of the substituent that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

[0025] R 3 Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a naphthylmethyl group. The aryl group contained in the aralkyl group may have a substituent, and examples of the substituent that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, and more preferably 7 to 15.

[0026] R 3Specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, and arylsulfinyl group are R 3 Reference is made to the description of aryl groups in

[0027] R 3 Examples of the heteroaryl group include a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyraridinyl group, a pyrimidinyl group, a pyridazinyl group, a thiazolyl group, an isothiazolyl group, a furanyl group, and a pyranyl group. The heteroaryl group may have a substituent, and examples of the substituent that the heteroaryl group has include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group, a nitro group, a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. The number of carbon atoms in the heteroaryl group is preferably 3 to 18, and more preferably 4 to 12.

[0028] R 3 The amino group of the formula: -NR 11 R 12 and R 11 and R 12 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are described above. Examples of the alkenyl group and the alkynyl group include the substituents in which part of the carbon-carbon single bond of the alkyl group described above is replaced with a double bond or a triple bond, and in these substituents, part of the hydrogen atoms may be replaced with a halogen atom. In addition, R 11 and R 12 may be linked to each other to form a ring.

[0029] R 3The amide group of the formula: -NH-C(=O)-R 13 and R 13 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are as described above, and some of the hydrogen atoms may be substituted with halogen atoms.

[0030] R 3 The sulfonamide group of the formula: -NH-SO2-R 14 and R 14 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group are as described above, and some of the hydrogen atoms may be substituted with halogen atoms.

[0031] R 3 Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0032] R 3 is preferably at least one selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group, and an arylthio group. 3 is a nitrogen-containing substituent, the substituent R 3 is decomposed or converted to another structure by heating or reaction, and the ethylene compound is likely to exhibit a color such as yellow, which is not very preferable. From the viewpoint of enabling the ethylene compound to be stable and absorb light in the ultraviolet to purple region, R 3 is preferably a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3. In particular, the four R 3 Among these, preferably two or more are hydrogen atoms, more preferably three or more are hydrogen atoms, and particularly preferably all four are hydrogen atoms.

[0033] In formula (2), X represents a sulfur atom or an oxygen atom, which stabilizes the ethylene compound and makes it easier to absorb light in the ultraviolet to violet region. From the viewpoint of effectively absorbing light in the UVA region, X is preferably a sulfur atom.

[0034] In the group A represented by formula (2), X may be bonded to the ortho-position, meta-position, or para-position relative to the ethylene structural unit. From the viewpoint of ease of production of the ethylene compound, X is preferably bonded to the para-position relative to the ethylene structural unit.

[0035] In formula (1), two or more groups A are bonded to the linking group L. By bonding two or more groups A to the linking group L, the heat resistance of the ethylene compound can be improved. The multiple groups A bonded to the linking group L may be the same or different from one another. The linking group L is an a-valent linking group that connects a number of groups A, and can be composed of, for example, a single divalent, trivalent, or tetravalent organic group for a linking group, or a combination of these divalent, trivalent, or tetravalent organic groups for a linking group. The number a of groups A bonded to the linking group L in 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 more preferably 3 or less, and particularly preferably 2.

[0036] Examples of the linking group L include alkylene groups, -O-, -S-, -SO-, methine groups (-C<) which may have an alkyl group, tetravalent linking groups of >C<, and linking groups combining these. In this case, the alkylene groups, -O-, -S-, and -SO- are divalent organic groups for linking groups, the methine groups (-C<) which may have an alkyl group are trivalent organic groups for linking groups, and >C< is a tetravalent organic group for linking groups. In ethylene compounds, multiple groups A are bonded to such linking groups L.

[0037] In the ethylene compound represented by formula (1), multiple groups A are linked to each other via a linking group L through six or more atoms. That is, multiple groups A are linked to each other via a linking group L, and multiple groups A are linked to each other via at least six atoms. Therefore, the linking group L has a portion where six or more atoms are connected in series between multiple groups A. When there are three or more groups A, it is preferable that each group A is linked to each other via six or more atoms through the linking group L. In the ethylene compound of the present invention, multiple groups A are linked to each other via six or more atoms through the linking group, so that the degree of freedom of movement of the linking group L is increased, and the group A can freely spread via the linking group L. Therefore, the above-mentioned COOR 1 R 1 In combination with an appropriate selection of the alkyl group, the affinity for organic solvents and resins is enhanced, and the solubility in organic solvents and resins can be increased. As a result, it becomes easy to incorporate the ethylene compound uniformly and at a high concentration in the resin composition, and even when forming an ultraviolet absorbing layer from the resin composition, even if the layer is formed to a thin thickness, it is possible to favorably absorb light in the ultraviolet to violet region due to the ethylene compound. The multiple groups A are preferably linked to each other via the linking group L via 7 or more atoms, more preferably 8 or more atoms, and preferably 20 or less, more preferably 17 or less, even more preferably 14 or less, and even more preferably 11 or less.

[0038] The alkylene group contained in the linking group L may be a linear or branched alkylene group. Examples of the alkylene group contained in the linking group L include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene. The alkylene group may have a substituent, such as a hydroxyl group and / or a thiol group.

[0039] In the linking group L, -O-, -S-, and -SO- are preferably not located at the terminals, and these organic groups for linking groups are preferably not consecutive. That is, -O-, -S-, and -SO- are preferably bonded on both sides with a tetravalent linking group such as an alkylene group, a methine group (-C<), or >C<. This can increase the stability of the ethylene compound represented by formula (1).

[0040] When the divalent linking group L is a divalent group formed by linking organic groups, examples of the divalent linking group L include a group in which an alkylene group, -O-, and an alkylene group are bonded in this order; a group in which an alkylene group, -S-, and an alkylene group are bonded in this order; a group in which an alkylene group, -SO-, and an alkylene group are bonded in this order; a group in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in this order; and a group in which an alkylene group, -S-, an alkylene group, -S-, and an alkylene group are bonded in this order.

[0041] Examples of the group in which an alkylene group, -O-, and another alkylene group are bonded in this order include dialkyl ether residues having a bond at the alkyl moiety, such as a group in which ethylene, -O-, and propylene are bonded in this order, a group in which propylene, -O-, and propylene are bonded in this order, a group in which methylene, -O-, and butylene are bonded in this order, and a group in which butylene, -O-, and butylene are bonded in this order.

[0042] Examples of the group in which an alkylene group, -S-, and another alkylene group are bonded in this order include dialkylthiol residues having bonds at the alkyl moiety, such as a group in which ethylene, -S-, and propylene are bonded in this order, a group in which propylene, -S-, and propylene are bonded in this order, a group in which methylene, -S-, and butylene are bonded in this order, and a group in which butylene, -S-, and butylene are bonded in this order.

[0043] Examples of the group in which an alkylene group, -SO-, and another alkylene group are bonded in this order include dialkyl sulfoxide residues having bonds in the alkyl moiety, such as a group in which ethylene, -SO-, and propylene are bonded in this order, a group in which propylene, -SO-, and propylene are bonded in this order, a group in which methylene, -SO-, and butylene are bonded in this order, and a group in which butylene, -SO-, and butylene are bonded in this order.

[0044] Examples of the group in which an alkylene group, -O-, an alkylene group, -O-, and an alkylene group are bonded in this order include alkylene glycol dialkyl ether residues having bonds on the alkyl moiety, such as a group in which methylene, -O-, ethylene, -O-, and methylene are bonded in this order, a group in which ethylene, -O-, ethylene, -O-, and ethylene are bonded in this order, and a group in which propylene, -O-, propylene, -O-, and propylene are bonded in this order.

[0045] Examples of the group in which an alkylene group, -S-, an alkylene group, -S-, and an alkylene group are bonded in this order include (alkylenedithio)dialkyl residues having bonds on the alkyl moiety, such as a group in which methylene, -S-, ethylene, -S-, and methylene are bonded in this order, a group in which ethylene, -S-, ethylene, -S-, and ethylene are bonded in this order, and a group in which propylene, -S-, propylene, -S-, and propylene are bonded in this order.

[0046] The trivalent or higher organic group for linking includes a methine group (-C<) or >C<, which may have an alkyl group. The alkyl group of the methine group is as defined above in R 2 Reference is made to the description of alkyl groups in the above.

[0047] Examples of the linking group L having a trivalent or higher organic group for linking groups include a group in which three of the divalent organic groups for linking groups are bonded to a methine group (for example, an alkanetriyl group in which three alkylene groups are bonded to a methine group), a group in which four of the divalent organic groups for linking groups are bonded to >C< (for example, an alkanetetrayl group in which four alkylene groups are bonded to >C<), a tetravalent organic group for linking groups in which two methine groups are bonded to a divalent organic group for linking groups, and groups bonded to the divalent organic groups for linking groups, a group in which five of the divalent organic groups for linking groups are bonded to a pentavalent organic group for linking groups in which three methine groups are linked, a group in which four of the divalent organic groups for linking groups are bonded to a tetravalent organic group for linking groups in which two methine groups are linked via the divalent organic group for linking groups, and a group in which five of the divalent organic groups for linking groups are bonded to a pentavalent organic group for linking groups in which three methine groups are linked via the divalent organic group for linking groups.

[0048] From the viewpoint of increasing the degree of freedom of movement of the ethylene compound, the linking group L is preferably an alkylene group, -O-, -S-, -SO, or a linking group formed by combining these groups, and more preferably a divalent linking group (i.e., a is 2 in formula (1)). In addition, the alkylene group preferably has no substituent.

[0049] The ethylene compound is preferably an ethylene compound represented by the following formula (3). Such an ethylene compound can effectively absorb light in the ultraviolet to violet region, has excellent solubility in organic solvents and resins, and is easy to produce. In the following formula (3), R 1a and R 1b The explanation of R above 1 The explanation of R 2a and R 2b The explanation of R above 2 The explanation of X is referred to. a and X b For an explanation of X, please refer to the explanation of X above.

[0050] [ka]

[0051] The ethylene compound represented by the above formula (3) is X a and X b is more preferably bonded to the para position of the ethylene structural unit, as represented by the following formula (3-1).

[0052] [ka]

[0053] The ethylene compound of the present invention preferably has a maximum absorption peak at a wavelength of 340 nm or more and 400 nm or less in its absorption spectrum measured in toluene in a wavelength range of 300 nm to 600 nm (more preferably, 300 nm to 700 nm, and even more preferably, 300 nm to 800 nm). That is, when the absorption spectrum of the ethylene compound is measured in toluene, it preferably has a peak with an absorption maximum in a wavelength range of 340 nm to 400 nm, and the absorption maximum of the absorption peak preferably has a maximum value in a wavelength range of 300 nm to 600 nm. If the ethylene compound exhibits such an absorption spectrum, it can effectively absorb light in the ultraviolet (UVA) to violet region, particularly UVA light at the longer wavelengths that penetrate the ozone layer and reach the earth's surface in greater amounts. The maximum wavelength of the absorption peak is more preferably 350 nm or more, more preferably 355 nm or more, and more preferably 390 nm or less, and even more preferably 380 nm or less.

[0054] When the absorbance at the maximum wavelength of the maximum absorption peak is taken as 1, the ethylene compound preferably has a peak width of 100 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less, at an absorbance of 0.5 of the absorption peak. If the ethylene compound exhibits such an absorption spectrum, it will be able to selectively absorb light in the ultraviolet (UVA) to violet region. The lower limit of the peak width is not particularly limited, but may be, for example, 20 nm or more, or 30 nm or more.

[0055] When the absorbance at the maximum wavelength of the maximum absorption peak is taken as 1, the ethylene compound preferably has an average absorbance in a wavelength range of 470 nm to 600 nm (preferably a wavelength range of 450 nm to 700 nm) of 0.03 or less, more preferably 0.02 or less, and even more preferably 0.01 or less, thereby enabling an increase in light transmittance over a wide range of the visible light region.

[0056] The absorption spectrum is determined by measuring absorbance at 1 nm intervals over a specified wavelength range. Absorbance values ​​at wavelengths less than the measurement interval (1 nm) are calculated by linear interpolation from absorbance measurements at 1 nm intervals. The concentration of ethylene compounds in toluene is adjusted so that the absorbance at the absorption maximum of the maximum absorption peak is 1 ± 0.003. The average absorbance in the wavelength range of 470 nm to 600 nm is determined by averaging the absorbance values ​​of 131 points measured at 1 nm intervals over the wavelength range of 470 nm to 600 nm.

[0057] The ethylene compound of the present invention can effectively absorb light in the ultraviolet (UVA) to violet region, and therefore can be suitably used as an ultraviolet absorber. The ultraviolet absorber may contain only one type of ethylene compound, or two or more types. The ultraviolet absorber may contain, in addition to the ethylene compound of the present invention, a known ultraviolet absorber (for example, a benzotriazole-based compound, a benzophenone-based compound, a salicylic acid-based compound, a benzoxazinone-based compound, a cyanoacrylate-based compound, a benzoxazole-based compound, a merocyanine-based compound, a triazine-based compound, etc.).

[0058] The ethylene compound of the present invention can be used by dissolving or dispersing it in any solvent (for example, water or an organic solvent). Therefore, the present invention also provides an ethylene compound solution containing the ethylene compound represented by formula (1) and a solvent. It is preferable to use an organic solvent as the solvent, which makes it possible to obtain an ethylene compound solution in which the ethylene compound is dissolved at a high concentration. The ethylene compound solution of the present invention can effectively absorb light in the ultraviolet (UVA) to violet region.

[0059] Examples of solvents used in the ethylene compound solution include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, propyl acetate, and butyl acetate; ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether; glycol derivatives (ether compounds, ester compounds, ether ester compounds, etc.) such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide; pyrrolidones such as N-methyl-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as cyclohexane and heptane. These solvents may be used alone or in combination of two or more.

[0060] The amount of solvent used may be appropriately determined depending on the desired concentration of the ethylene compound in the ethylene compound solution. The concentration of the ethylene compound in the ethylene compound solution is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, thereby enabling the production of an ethylene compound solution with a high ethylene compound concentration. The upper limit of the ethylene compound concentration in the ethylene compound solution is appropriately determined depending on the solubility of the ethylene compound in the solvent, and may be, for example, 50% by mass or less, 40% by mass or less, or 30% by mass or less.

[0061] The ethylene compound solution may further contain a near-infrared absorbing dye and / or a visible light absorbing dye. If the ethylene compound solution further contains a near-infrared absorbing dye and / or a visible light absorbing dye, it can effectively absorb light in the red to near-infrared region and / or light in the visible light region in addition to light in the ultraviolet to purple region. For details about the near-infrared absorbing dye and the visible light absorbing dye, see the explanation of the near-infrared absorbing dye and the visible light absorbing dye that can be contained in the resin composition described below.

[0062] Next, an example of a method for producing an ethylene compound according to the present invention will be described with reference to the following scheme. Note that the following scheme does not limit the method for producing an ethylene compound according to the present invention, and the ethylene compound according to the present invention may be produced by other schemes.

[0063] The ethylene compound of the present invention can be produced, for example, according to the scheme shown below. That is, in step [S-1], a benzaldehyde compound of formula (4) is reacted with a cyanoacetate of formula (8) to obtain a compound of formula (5) that provides group A. Then, in step [S-2], the compound of formula (5) is reacted with a compound of formula (9) that provides linking group L to obtain a compound of formula (7) in which group A is bonded to linking group L, i.e., the ethylene compound of the present invention. Alternatively, in step [S-3], a benzaldehyde compound of formula (4) is reacted with a compound of formula (9) that provides linking group L to obtain a compound of formula (6) in which a precursor of group A is bonded to linking group L. Then, in step [S-4], the compound of formula (6) is reacted with a cyanoacetate of formula (8) to obtain a compound of formula (7) in which group A is bonded to linking group L, i.e., the ethylene compound of the present invention.

[0064] [ka]

[0065] In the above scheme, R 1 ~R 3 , X, and L have the same meanings as in the above formula (1) and formula (2), and the preferred embodiments thereof are also as explained above. 1 and Z 2 represents a halogen atom -Y and the other represents -XH, and Z 1 and Z 2 The combination of Z 1 is a halogen atom -Y, and Z 2 is -XH or Z 1 is -XH and Z 2 is a halogen atom -Y.

[0066] The ethylene compound of the present invention represented by formula (7) can be obtained by a production method including a step (step [S-1]) of subjecting a benzaldehyde compound of formula (4) and a cyanoacetate of formula (8) to a Knoevenagel condensation reaction to obtain a compound of formula (5), and a step (step [S-2]) of reacting a compound of formula (5) with a compound of formula (9) to nucleophilic substitution of X (a sulfur atom or an oxygen atom) contained in one of the compounds of formula (5) and formula (9) with a halogen atom Y contained in the other compound. In step [S-2], X (a sulfur atom or an oxygen atom) contained in one of the compounds of formula (5) and formula (9) nucleophilically acts on the carbon atom adjacent to the halogen atom Y contained in the other compound, thereby causing a nucleophilic substitution reaction between the compound of formula (5) and the compound of formula (9), and obtaining a compound of formula (7) in which a group A is bonded to a linking group L.

[0067] Step [S-1] is a reaction of a benzaldehyde compound of formula (4) with a compound of formula: NC-CH-COOR 4 (R 4 is esterified to form R 1 This step can also be replaced with step [S-1'] of obtaining the compound of formula (5) by subjecting a cyanoacetic acid derivative represented by the formula (I) to a Knoevenagel condensation reaction and esterification.

[0068] The ethylene compound of the present invention represented by formula (7) can also be obtained by a production method including a step (step [S-3]) of reacting a benzaldehyde compound of formula (4) with a compound of formula (9) to nucleophilically substitute X (a sulfur atom or an oxygen atom) contained in one of the compounds of formula (4) and formula (9) with a halogen atom Y contained in the other compound to obtain a compound of formula (6), and a step (step [S-4]) of subjecting the compound of formula (6) to a Knoevenagel condensation reaction with a cyanoacetate ester of formula (8). In step [S-3], X (a sulfur atom or an oxygen atom) contained in one of the compounds of formula (4) and formula (9) nucleophilically acts on the carbon atom adjacent to the halogen atom Y contained in the other compound, thereby causing a nucleophilic substitution reaction between the compound of formula (4) and the compound of formula (9), thereby obtaining a compound of formula (6) in which a precursor of group A is bonded to the linking group L.

[0069] Step [S-4] is a reaction of a compound of formula (6) with a compound of formula: NC-CH2-COOR 4 (R 4 is esterified to form R 1 This step can also be replaced with step [S-4'] of obtaining the compound of formula (7) by subjecting a cyanoacetic acid derivative represented by the formula (7) to a Knoevenagel condensation reaction with a cyanoacetic acid derivative represented by the formula (7)

[0070] As the compound of formula (9), Z 2Compounds in which is -XH include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 6-mercapto-1-hexanol, 7-mercapto-1-hexanol, 8-mercapto-1-hexanol, triethylenediamine, 1,6-hexanediol, 1,7-heptanediol ... triethylene Ethylene glycol, tetraethylene glycol, 1,2-bis(2-mercaptoethoxy)ethane, 1,3-bis(2-mercaptoethoxy)propane, 1,3-bis(2-mercaptopropoxy)propane, 1,2-bis(2-mercaptoethylthio)ethane, 1,3-bis(2-mercaptoethylthio)propane, 1,2-bis(2-hydroxyethylthio)ethane, 1,3-bis(2-hydroxyethylthio)propane, di(3-hydroxypropyl)sulfonyl compounds providing a divalent linking group L, such as 1,7-dihydroxy-4-(2-hydroxyethyl)heptane, 1,7-dimercapto-4-(2-mercaptoethyl)heptane, 1,7-dihydroxy-4-(2-mercaptoethyl)heptane, 1,7-dihydroxy-4-(3-hydroxypropyl)heptane, 1,7-dihydroxy-4-(2-mercaptoethyl)heptane, 1,7-dihydroxy-4-(3-hydroxypropyl)heptane, 1,7-dihydroxy-4-(2-hydroxyethyl)heptane, 1,7-dihydroxy-4-(2-mercaptoethyl)heptane, 1,7-dihydroxy-4-(3-hydroxypropyl)heptane, 1,7-dihydroxy-4-(2-hydroxyethyl)heptane, 1,7-dihydroxy-4-(2-hydroxyethyl)heptane, 1,7-dihydroxy-4-(2-hydroxypropyl)heptane, 1,7-dihydroxy-4-(3-hydroxypropyl)heptane, 1,7-dihydroxy-4-(2-hydroxyethyl ... and compounds that provide a tetravalent linking group L such as 1,8-dihydroxy-3,4-bis(2-hydroxyethyl)octane, 1,8-dimercapto-3,4-bis(2-mercaptoethyl)octane, 1,8-dihydroxy-3,4-bis(2-mercaptoethyl)octane, and 1,8-dihydroxy-3,4-bis(2-hydroxypropyl)octane. 2 The compounds in which Y is a halogen atom include the compounds exemplified above as Z 2 is —XH in the compound of formula (9), where —XH is replaced with a halogen atom.

[0071] The above reaction is preferably carried out in the presence of a solvent. Examples of solvents that can be used include chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; chlorinated aromatics such as chlorotoluene and dichlorobenzene; ethers such as tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, diisopropyl ether, and diethyl ether; nitriles such as acetonitrile, propionitrile, acrylonitrile, and butyronitrile; and alcohols such as methanol, ethanol, propanol, and butanol. These solvents may be used alone or in combination of two or more.

[0072] In the above reaction, the reaction temperature may be set appropriately, for example, preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and preferably 200°C or lower, more preferably 150°C or lower. The reaction may be carried out under reflux. The reaction time is not particularly limited and may be set appropriately depending on the progress of the reaction, but is, for example, preferably 0.5 hours or higher, more preferably 1 hour or higher, and preferably 48 hours or lower, more preferably 24 hours or lower. In step [S-1] or step [S-4], the reaction is preferably carried out under an inert gas (nitrogen, argon, etc.) atmosphere.

[0073] The resulting ethylene compound may be appropriately purified, if necessary, by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation, recrystallization, or crystallization.

[0074] The ethylene compound of the present invention can be mixed with a resin component to form a resin composition. Since the ethylene compound of the present invention has excellent solubility in resins, the ethylene compound can be contained at a high concentration in the resin composition. Since the ethylene compound of the present invention also has excellent solubility in organic solvents, when producing a resin composition, the ethylene compound can be dissolved in an organic solvent to prepare an ethylene compound solution, and this can be mixed with the resin component, thereby easily making the ethylene compound present uniformly and at a high concentration in the resin composition.

[0075] The resin composition containing the ethylene compound of the present invention can suppress deterioration caused by light in the ultraviolet (UVA) to violet region, and can be used as an optical filter that cuts light in the ultraviolet (UVA) to violet region by curing the resin composition to form a resin molded product such as a film or a sheet-shaped molded product. By using the ethylene compound of the present invention, the ethylene compound can be present in a high concentration in the resin composition, making it possible to form an optical filter that is thin and that favorably absorbs light in the ultraviolet (UVA) to violet region.

[0076] The ethylene compound of the present invention also has excellent heat resistance, and therefore can suitably exhibit its ultraviolet absorbing effect, even when, for example, it is blended with a thermoplastic resin and the resulting resin is heat-molded. Furthermore, even when the resin composition or a resin molded article is exposed to ultraviolet light during storage or during the production and processing of an optical filter (for example, vapor deposition or mounting), it is expected to protect the resin component and other components contained in the resin composition (such as the near-infrared absorbing dye described below) from the ultraviolet light and suppress deterioration of these components.

[0077] The resin composition contains at least the ethylene compound of the present invention and a resin component. The ethylene compound contained in the resin composition may be one type only, or two or more types. The resin composition may further contain other ultraviolet absorbers (e.g., benzotriazole-based compounds, benzophenone-based compounds, salicylic acid-based compounds, benzoxazinone-based compounds, cyanoacrylate-based compounds, benzoxazole-based compounds, merocyanine-based compounds, triazine-based compounds, etc.).

[0078] In order to achieve the desired performance, the content of the ethylene compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.1% by mass or more, based on 100% by mass of the solid content of the resin composition. Furthermore, in order to improve the moldability and film-forming properties of the resin composition, the content of the ethylene compound in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the solid content of the resin composition. When the resin composition also contains other UV absorbers, the total content of these is preferably within the above range. The content of the other UV absorbers is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 30 parts by mass or less, based on 100 parts by mass of the ethylene compound. The solid content of the resin composition refers to the amount of the resin composition excluding the solvent, when the resin composition contains a solvent.

[0079] Known resins can be used as the resin component contained in the resin composition. The resin component is preferably one that is highly transparent and capable of dissolving or dispersing the ethylene compound of the present invention. When the resin composition also contains a near-infrared absorbing dye and / or a visible light absorbing dye as described below, the resin component is preferably one that can also dissolve or disperse the dye. By selecting such a resin component, it is possible to achieve both high transmittance in the wavelength range that is desired to be transmitted and high absorbance in the wavelength range that is desired to be blocked.

[0080] The resin component may be not only a polymerized resin, but also a resin raw material (including a resin precursor, raw materials for the precursor, a monomer constituting the resin, etc.) that is incorporated into the resin through a polymerization reaction or a crosslinking reaction when the resin composition is molded. In the present invention, any resin is included in the resin component. In the latter case, the structure of the ethylene compound may be partially or completely decomposed by unreacted substances, reactive terminal functional groups, ionic groups, catalysts, acidic or basic groups, etc. present in the reaction liquid obtained by the polymerization reaction. Therefore, if such a concern exists, it is desirable to form the resin composition by blending an ethylene compound with a polymerized resin.

[0081] It is preferable to use a highly transparent resin as the resin component, which allows the properties of the ethylene compound contained in the resin composition to be suitably utilized. Examples of the resin component include (meth)acrylic resins, (meth)acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (e.g., polyethylene resins, polypropylene resins), cycloolefin resins, melamine resins, urethane resins, styrene resins, polyvinyl acetate, polyamide resins (e.g., nylon), aramid resins, polyimide resins, polyamideimide resins, alkyd resins, phenolic resins, epoxy resins, polyester resins (e.g., polybutylene terephthalate (PBT) resins, polyethylene terephthalate (PET) resins, polyarylate resins, etc.), polysulfone resins, butyral resins, polycarbonate resins, and the like. Examples of the resin include ether resins, ABS resins (acrylonitrile butadiene styrene resins), AS resins (acrylonitrile-styrene copolymers), silicone resins, modified silicone resins (e.g., (meth)acrylic silicone resins, alkyl polysiloxane resins, silicone urethane resins, silicone polyester resins, and silicone acrylic resins), and fluorine-based resins (e.g., fluorinated aromatic polymers, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluorine resins (PFA), fluorinated polyaryl ether ketones (FPEK), fluorinated polyimides (FPI), fluorinated polyamic acids (FPAA), and fluorinated polyether nitriles (FPEN)). Among these, polyimide resins, polyamide-imide resins, (meth)acrylic resins, cycloolefin resins, epoxy resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, polysulfone resins, and fluorinated aromatic polymers are preferred from the viewpoints of excellent transparency and heat resistance.

[0082] Polyimide resins are polymers containing imide bonds in the repeating units of the main chain, and can be produced, for example, by condensation polymerization of tetracarboxylic dianhydride and diamine to obtain polyamic acid, which is then dehydrated and cyclized (imidized). Aromatic polyimides in which aromatic rings are linked by imide bonds are preferably used as the polyimide resin. Examples of polyimide resins that can be used include Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc., Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Inc., Merdin (registered trademark) manufactured by Saint-Gobain, and the TPS (registered trademark) TI3000 series manufactured by Toray Plastics Precision Co., Ltd.

[0083] Polyamide-imide resins are polymers containing amide bonds and imide bonds in the repeating units of the main chain. Examples of polyamide-imide resins that can be used include Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Viromax (registered trademark) manufactured by Toyobo Co., Ltd., and TPS (registered trademark) TI5000 series manufactured by Toray Plastics Seiko Co., Ltd.

[0084] The (meth)acrylic resin is a polymer having a repeating unit derived from (meth)acrylic acid or a derivative thereof, and for example, a resin having a repeating unit derived from a (meth)acrylic acid ester, such as a poly(meth)acrylic acid ester resin, is preferably used. The (meth)acrylic resin also preferably has a ring structure in the main chain, such as a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, or a maleimide ring structure, which contains a carbonyl group; or an oxetane ring structure, an azetidine ring structure, a tetrahydrofuran ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, or a piperidine ring structure, which does not contain a carbonyl group. The carbonyl group-containing ring structure also includes a structure containing a carbonyl group derivative group, such as an imide group. Examples of (meth)acrylic resins having a carbonyl group-containing ring structure that can be used include those described in JP-A Nos. 2004-168882, 2008-179677, WO 2005 / 54311, and 2007-31537.

[0085] The cycloolefin resin is a polymer obtained by polymerizing a cycloolefin as at least a part of the monomer component, and is not particularly limited as long as it has an alicyclic structure in a part of the main chain. Examples of the cycloolefin resin that can be used include Topas (registered trademark) manufactured by Polyplastics Co., Ltd., Apel (registered trademark) manufactured by Mitsui Chemicals, Inc., Zeonex (registered trademark) and Zeonor (registered trademark) manufactured by Nippon Zeon Co., Ltd., and Arton (registered trademark) manufactured by JSR Corporation.

[0086] Epoxy resins are resins that can be cured by crosslinking an epoxy compound (prepolymer) in the presence of a curing agent or curing catalyst. Examples of epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, and hydrogenated epoxy compounds. Examples of such compounds include fluorene epoxy (Oxol (registered trademark) PG-100) manufactured by Osaka Gas Chemicals Co., Ltd., bisphenol A epoxy compound (JER (registered trademark) 828EL) and hydrogenated bisphenol A epoxy compound (JER (registered trademark) YX8000) manufactured by Mitsubishi Chemical Corporation, and alicyclic liquid epoxy compound (Celloxide (registered trademark) 2021P) manufactured by Daicel Corporation.

[0087] Polyester resins are polymers containing ester bonds in the repeating units of the main chain, and can be obtained, for example, by condensation polymerization of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Examples of polyester resins that can be used include the OKP series manufactured by Osaka Gas Chemical Co., Ltd., the TRN series manufactured by Teijin Limited, Teonex (registered trademark), Rynite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Novaduran (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, and Lumirror (registered trademark) and Toraycon (registered trademark) manufactured by Toray Industries, Inc.

[0088] Polyarylate resins are polymers obtained by polycondensation of a dihydric phenol compound and a dibasic acid (e.g., an aromatic dicarboxylic acid such as phthalic acid), and have a repeating unit containing an aromatic ring and an ester bond in the repeating unit of the main chain. Examples of polyarylate resins that can be used include Vectran (registered trademark) manufactured by Kuraray Co., Ltd., and U Polymer (registered trademark) and Unifiner (registered trademark) manufactured by Unitika Ltd.

[0089] Polyamide resins are polymers containing amide bonds in the repeating units of their main chains, and can be obtained, for example, by condensation polymerization of diamines and dicarboxylic acids. Polyamide resins may have an aliphatic skeleton in their main chains, and nylon, for example, can be used as such an amide resin. Polyamide resins may have an aromatic skeleton, and aramid resins are known as such polyamide resins. Aramid resins are preferably used because of their excellent heat resistance and high mechanical strength, and examples of such resins include Twaron (registered trademark) and Conex (registered trademark) manufactured by Teijin Limited, and Kevlar (registered trademark) and Nomex (registered trademark) manufactured by DuPont.

[0090] Polycarbonate resin is a polymer containing a carbonate group (-O-(C=O)-O-) in the repeating unit of the main chain. Examples of polycarbonate resins that can be used include Panlite (registered trademark) manufactured by Teijin Limited, Iupilon (registered trademark), Novarex (registered trademark), and Zanter (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, and SD Polyca (registered trademark) manufactured by Sumika Styron Polycarbonate Co., Ltd.

[0091] The polysulfone resin is a polymer having a repeating unit containing an aromatic ring, a sulfonyl group (—SO—), and an oxygen atom. Examples of the polysulfone resin that can be used include Sumikaexcel (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., and UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers.

[0092] The fluorinated aromatic polymer is a polymer having a repeating unit containing an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond, and among these, a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferred. As the fluorinated aromatic polymer, for example, those described in JP 2008-181121 A can be used.

[0093] The resin component preferably has high transparency, which makes the resin composition more suitable for optical applications. The resin component preferably has a total light transmittance of 75% or more at a thickness of 0.1 mm, more preferably 80% or more, and even more preferably 85% or more. The upper limit of the total light transmittance of the resin component is not particularly limited, and the total light transmittance may be 100% or less, but may be, for example, 95% or less. The total light transmittance is measured in accordance with JIS K 7105.

[0094] The resin component preferably has a high glass transition temperature (Tg), which can improve the heat resistance of the resin composition and various molded articles obtained therefrom. The glass transition temperature of the resin component is, for example, preferably 110°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. There are no particular limitations on the upper limit of the glass transition temperature of the resin component, but in order to ensure the moldability of the resin composition, it is preferably, for example, 380°C or lower.

[0095] The resin composition may contain a near-infrared absorbing dye and / or a visible light absorbing dye. If the resin composition further contains a near-infrared absorbing dye and / or a visible light absorbing dye, an optical filter having light selective transmission properties can be obtained from the resin composition. For example, when the resin composition contains the ethylene compound of the present invention and a near-infrared absorbing dye, it can be used as a resin composition for a light selective transmission filter that suppresses transmission of light in the ultraviolet to purple region and the red to near-infrared region and preferentially transmits light in the visible region. When the resin composition contains the ethylene compound of the present invention and a visible light absorbing dye, it can be used as a resin composition for a colored filter, a blue light reduction filter, or the like.

[0096] The near-infrared absorbing dye preferably has an absorption maximum in the wavelength range of 600 nm to 1100 nm. More preferably, the near-infrared dye has an absorption peak in the wavelength range of 600 nm to 1100 nm in its absorption spectrum in the wavelength range of 450 nm to 1100 nm, and the absorption maximum of the absorption peak reaches its maximum value in the wavelength range of 450 nm to 1100 nm. The absorption maximum wavelength is more preferably 630 nm or longer, even more preferably 660 nm or longer, and more preferably 1000 nm or shorter, even more preferably 900 nm or shorter, and even more preferably 800 nm or shorter.

[0097] The visible light absorbing dye can be any dye that has a maximum absorption wavelength of the maximum absorption peak in the visible light region (for example, a wavelength range of more than 420 nm and less than 680 nm) without any particular limitation. In particular, it is preferable to use a visible light absorbing dye that has a maximum absorption wavelength of the maximum absorption peak in the wavelength range of 500 nm or more and less than 680 nm, where visibility is high.

[0098] The near-infrared absorbing dye and the visible light absorbing dye may be organic dyes, inorganic dyes, or organic-inorganic composite dyes (e.g., organic compounds with coordinated metal atoms or ions). Examples of near-infrared absorbing dyes and visible light absorbing dyes include squarylium dyes, croconium dyes, cyclic tetrapyrrole dyes (e.g., porphyrins, chlorins, phthalocyanines, naphthalocyanines, and cholines) that may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as a central metal ion, cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterrylene dyes, diimonium dyes, perylene dyes, quinacrylonitrile dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, and copper ion dyes. These dyes may be used alone or in combination of two or more. Among these, it is preferable to use at least one selected from squarylium dyes, croconium dyes, phthalocyanines, cyanine dyes, and dipyrromethene dyes as the near-infrared absorbing dye and visible light absorbing dye, because they can effectively absorb light of desired wavelengths. It is preferable to use at least one selected from squarylium dyes, croconium dyes, phthalocyanines, and cyanine dyes as the near-infrared absorbing dye. This makes it easy to effectively absorb light in the near-infrared region and increase the visible light transmittance.

[0099] The content of the near-infrared absorbing dye and the visible light absorbing dye in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.1% by mass or more, based on 100% by mass of the solid content of the resin composition, in order to achieve the desired performance. Furthermore, in order to improve the moldability and film-forming properties of the resin composition, the content of the near-infrared absorbing dye and the visible light absorbing dye in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the solid content of the resin composition. The total content of the ethylene compound, the near-infrared absorbing dye, and the visible light absorbing dye (or the total content including other ultraviolet absorbers) is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the solid content of the resin composition.

[0100] When the resin composition is used as a resin composition for a light selective transmission filter that preferentially transmits light in the visible light region, it is preferable to use, as the near-infrared absorbing dye, a squarylium compound represented by the following formula (11) or a croconium compound represented by the following formula (12). In the following formulas (11) and (12), R 21 ~R 24 each independently represents a group represented by the following formula (13) or formula (14).

[0101] [ka]

[0102] [ka]

[0103] In formula (13), ring P represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, which may have a substituent; R 31 ~R 33 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 32 and R 33may be linked to each other to form a ring. 34 ~R 38 each independently represents a hydrogen atom, an organic group, or a polar functional group; R 34 and R 35 , R 35 and R 36 , R 36 and R 37 , R 37 and R 38 may be linked to each other to form a ring. * represents the bonding site to the 4-membered ring in formula (11) or the 5-membered ring in formula (12).

[0104] R 31 ~R 38 For details of the organic groups and polar functional groups, see above R 3 Please refer to the explanation of organic groups and polar functional groups in R. 31 ~R 38 is an independent group, R 31 ~R 38 are each preferably independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an amino group, an amido group, or a hydroxy group. Details of these groups are given in the above R 3 Reference is made to the explanation regarding

[0105] R 32 ~R 38Examples of the ring structures formed from the above include hydrocarbon rings and heterocycles. These ring structures may or may not have aromaticity, but are preferably non-aromatic hydrocarbon rings or non-aromatic heterocycles. Examples of non-aromatic hydrocarbon rings include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; and cycloalkenes such as cyclopentene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of non-aromatic heterocycles include rings in which one or more carbon atoms constituting the hydrocarbon ring as described above are replaced with at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of non-aromatic heterocycles include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholine ring, a hexamethyleneimine ring, a hexamethylene oxide ring, a hexamethylene sulfide ring, and a heptamethyleneimine ring.

[0106] In the group of formula (13), R 32 and R 33 The ring structure formed by linking the groups is preferably a 4- to 9-membered unsaturated hydrocarbon ring, and among these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are more preferred. When the group of formula (13) is configured in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharper.

[0107] Examples of the aromatic hydrocarbon ring of ring P in formula (13) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, and a cyclotetradecaheptaene ring. The aromatic hydrocarbon ring may have only one ring structure or may be a ring structure in which two or more ring structures are fused. The aromatic heterocycle of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in the ring structure and has aromaticity, such as a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a purine ring, and a pteridine ring. The aromatic heterocycle may have only one ring structure or may be a ring structure in which two or more ring structures are fused. The fused ring containing these ring structures of ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused together, and examples thereof include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, a benzopyran ring, an acridine ring, a xanthene ring, a carbazole ring, etc. By appropriately setting the π-conjugated system of ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

[0108] The ring P may have a substituent, and examples of the substituent include the organic groups and polar functional groups explained above. When the ring P has a substituent, the number of the substituents is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The ring P may not have a substituent.

[0109] For details of the squarylium compound and croconium compound having the group of formula (13), see the description in JP 2016-74649 A.

[0110] In the group represented by formula (14), R 35 and R 36 are preferably linked to form a ring, and further R 36 and R 37 may be linked to form a ring. In this case, at least R 34 and R 38becomes an independent group. If the group of formula (14) is configured in this way, the absorption peak in the red to near-infrared region becomes sharp. 35 and R 36 Ring structures formed from R 36 and R 37 The number of ring members in the ring structure formed by is preferably 5 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0111] In the group represented by formula (14), R 36 is an amino group or R is an amino group 36 R 35 and R to form a ring, or 37 In this case, the absorption maximum wavelength is shifted to the long wavelength side (for example, 685 nm or more), the transmittance of light in the red region is increased, and the color of the transmitted light can be made closer to the actual color.

[0112] In the squarylium compound and croconium compound having a group represented by formula (14), the benzene rings on both sides of the squarylium skeleton or the croconium skeleton may be linked by a linking group. Examples of such compounds include the squarylium compounds disclosed in JP 2015-176046 A.

[0113] The resin composition may contain a solvent. For example, when the resin composition is a resin composition in the form of a paint, the inclusion of a solvent makes it easier to apply the resin composition. A resin composition in the form of a paint can be obtained, for example, by dissolving an ethylene compound in a solvent containing a resin component, or by dispersing an ethylene compound in a solvent (dispersion medium) containing a resin component. The solvent may function as a solvent (dispersion medium) for the ethylene compound, or may function as a dispersion medium, but is preferably one that functions as the former. As the solvent, the solvents that can be used for the ethylene compound solution described above can be used.

[0114] The content of the solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and preferably less than 100% by mass, more preferably 95% by mass or less, based on 100% by mass of the resin composition. By adjusting the content of the solvent within this range, it becomes easy to obtain a resin composition with a high concentration of ethylene compounds.

[0115] The resin composition may contain a surface conditioner, which can prevent appearance defects such as striations and dents from occurring in the resin layer when the resin composition is cured to form a resin layer. The type of surface conditioner is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, etc. can be used. Examples of surface conditioners that can be used include the BYK (registered trademark) series manufactured by BYK-Chemie and the KF series manufactured by Shin-Etsu Chemical Co., Ltd.

[0116] The resin composition may contain a dispersant, which stabilizes the dispersibility of the ethylene compound or pigment even if the ethylene compound or pigment is partially dispersed in the resin composition, thereby preventing reaggregation of the ethylene compound or pigment. The type of dispersant is not particularly limited, and examples that can be used include the EFKA series manufactured by EFKA Additives, the BYK (registered trademark) series manufactured by BYK-Chemie, the Solsperse (registered trademark) series manufactured by The Lubrizol Corporation, the Disparlon (registered trademark) series manufactured by Kusumoto Chemicals, the Ajisper (registered trademark) series manufactured by Ajinomoto Fine-Techno Co., Ltd., the KP series manufactured by Shin-Etsu Chemical Co., Ltd., the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd., the Megafac (registered trademark) series manufactured by DIC Corporation, and the Disper Aid series manufactured by San Nopco.

[0117] The resin composition may contain a silane coupling agent or its hydrolyzate or hydrolyzed condensate. This can improve the adhesion of the resin layer to the support when the resin composition is cured on the support to form a resin layer. Examples of the silane coupling agent include silane coupling agents containing an epoxy group, an amino group, or a mercapto group, and among these, epoxy group-containing silane coupling agents are preferred. The use of such a silane coupling agent, combined with the inclusion of an ethylene compound in the resin composition, can improve the adhesion of the resin layer to the substrate. As the epoxy group-containing silane coupling agent, a compound having an epoxy group and an alkoxysilyl group can be used. The epoxy group-containing silane coupling agent may contain only one or more epoxy groups, and may contain only one or more alkoxysilyl groups.

[0118] A hydrolyzate of a silane coupling agent can be obtained by converting an alkoxysilyl group contained in the silane coupling agent into a silanol group by hydrolysis. A hydrolyzed condensate of a silane coupling agent can be obtained by dehydrating and condensing the silanol group contained in the hydrolyzed silane coupling agent to form a siloxane bond (-Si-O-Si-). Usually, when a silane coupling agent is hydrolyzed, a hydrolyzed condensate of the silane coupling agent is obtained, and a dehydration condensation reaction of the silanol group contained in the hydrolyzed silane coupling agent also occurs, so that a hydrolyzed condensate of the silane coupling agent can also be easily obtained. The hydrolyzed condensate of a silane coupling agent may be a dehydration condensate of a hydrolyzed silane coupling agent of the same kind, or may be a dehydration condensate of a hydrolyzed silane coupling agent of a different kind.

[0119] The resin composition may contain various additives, such as plasticizers, surfactants, viscosity modifiers, thickening / gelling inhibitors, dehydrating agents, antifoaming agents, preservatives, resistivity modifiers, etc. Furthermore, the resin composition may contain curing catalysts and curing rate modifiers for curing the resin components.

[0120] The resin composition can be cured to form a cured product. The resin composition may be one that is cured by a reaction of the resin components (for example, a polymerization reaction or a crosslinking reaction), or one that is cured by removing the solvent contained in the resin composition. Examples of such resin compositions that can be used include thermoplastic resin compositions that can be molded by injection molding, extrusion molding, etc., and resin compositions that have been made into paints that can be applied by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, screen printing, flexographic printing, inkjet printing, etc.

[0121] When the resin composition is a thermoplastic resin composition, a cured product can be obtained by subjecting the resin composition to injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this method, a thermoplastic resin is used as the resin component, and an ethylene compound is blended with the thermoplastic resin and then heat-molded to obtain a molded product. For example, the ethylene compound may be added to powder or pellets of the base resin, heated to about 150°C to 350°C, dissolved, and then molded. Furthermore, when kneading the resin, additives typically used in resin molding, such as plasticizers, may be added.

[0122] The shape of the cured product (molded product) is not particularly limited, but examples include planar (film, sheet, plate), granular, powdery, lump, particle aggregate, spherical, oval sphere, lens, cubic, columnar, rod, cone, cylinder, needle, fiber, hollow fiber, porous, etc.

[0123] When the resin composition is a paint-formed resin composition, a liquid or paste-like resin composition containing an ethylene compound and a resin component can be applied to a support (e.g., a resin plate, a film, a glass plate, etc.) to obtain a film-like cured product having a thickness of 200 μm or less or a sheet-like cured product having a thickness of more than 200 μm. The cured product thus obtained can be peeled from the support and handled as a film or sheet, or can be handled integrally with the support.

[0124] 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 multiple resin layers. When the cured product is handled as an integral part of a support, the cured product may be formed on only one side of the support, or on both sides. Note that the cured product and support may also be integrated by thermocompression bonding or chemical bonding a molded product formed from the resin composition to the support.

[0125] Because the ethylene compound of the present invention has excellent heat resistance, it can preferably exhibit its ultraviolet absorbing effect even when it is blended with a thermoplastic resin and then heated and molded, or when it is integrated with a support by thermocompression bonding or chemical bonding. Furthermore, even when molding is performed using a resin that requires a thermosetting reaction at high temperatures (e.g., a polyimide precursor, an epoxy resin, an acrylic resin, etc.) or a resin that requires drying at high temperatures (e.g., a resin containing a high-boiling point solvent or a resin with a high glass transition temperature), the excellent heat resistance of the ethylene compound allows it to preferably exhibit its ultraviolet absorbing effect.

[0126] The ultraviolet absorber or resin composition containing the ethylene compound of the present invention, and a cured product thereof can be used for building materials such as coated glass, resin glass, and interior and exterior materials, paints, adhesives, automobile parts, containers for holding food, medicines, cosmetics, chemicals, and the like, various films (protective films, optical films, retardation films, packaging films, agricultural films, and the like), various lenses (sunglasses, goggles, blue light-blocking glasses, medical protective glasses, and the like), telephone cable sheath materials used in electric wires, and the like, members for irradiation devices that use ultraviolet light as a light source, fibers, display members, touch panels, optical filter members, optical sensor members, surface protective members such as cover glass and cover panels, filter members that remove rays harmful to the human body, various sensor members (including those for preventing malfunction), lighting members, solar cell members, signs, and labels.

[0127] The resin composition of the present invention can be preferably used as a resin composition for forming filters used in various applications such as optical devices, display devices, mechanical parts, electric and electronic parts, etc. The resin composition can be applied to optical filters such as ultraviolet cut filters and selective light transmission filters that preferentially transmit light in the visible light region.

[0128] Imaging devices such as mobile phone cameras, digital cameras, car cameras, video cameras, and display elements (LEDs, etc.) typically use imaging elements that convert light from a subject into electrical signals and output the signals, and these imaging elements are equipped with light-receiving elements such as CCDs (Charge Coupled Devices) and CMOSs ​​(Complementary Metal-Oxide Semiconductors), as well as lenses, and, to improve performance, are also equipped with light-selective transmission filters for removing optical noise (e.g., ghosts and flares) that interfere with image processing, etc. Such light-selective transmission filters are typically provided with a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately stacked, and the dielectric multilayer film can block incident light in a desired wavelength range by adjusting the thickness of each of the high-refractive index material layers and the low-refractive index material layers.

[0129] However, because the cutoff wavelength range or transmission wavelength range of a dielectric multilayer film changes depending on the angle of incidence, changing the angle of incidence from perpendicular to oblique shifts the cutoff wavelength range or transmission wavelength range toward shorter wavelengths. Therefore, for obliquely incident light, a dielectric multilayer film may not be able to adequately cut light in the desired wavelength range, or it may also cut light in the visible light range, resulting in a shift in color. In particular, in recent years, there has been a strong demand for image sensors to be smaller and thinner. This has led to a decrease in the distance between the lens and the light-receiving element, which means that the light-receiving element must receive light incident from more oblique angles. In this case, the cutoff wavelength range or transmission wavelength range becomes more dependent on the angle of incidence, resulting in a noticeable shift toward shorter wavelengths of light in the short wavelength range, i.e., light in the ultraviolet to violet range, which was previously barely affected.

[0130] The resin composition of the present invention contains the ethylene compound described above. This ethylene compound exhibits a sharp absorption peak in the ultraviolet (UVA) to violet region. Therefore, an optical filter formed from this resin composition can selectively absorb light in the ultraviolet (UVA) to violet region and reduce incident angle dependence on the short wavelength side of the visible light region. In particular, the ethylene compound of the present invention can effectively absorb relatively long wavelength UVA light (e.g., wavelengths in the range of 340 nm to 400 nm). Therefore, an optical filter formed from the resin composition of the present invention has a cut wavelength range near the boundary between the visible light region and the ultraviolet region, thereby effectively reducing incident angle dependence on the short wavelength side of the visible light region. If the resin composition of the present invention further contains a near-infrared absorbing dye in addition to the ethylene compound, an optical filter formed from this resin composition can reduce incident angle dependence on both the short wavelength side and the long wavelength side of the visible light region. Moreover, because the ethylene compound contained in the optical filter has excellent heat resistance, decomposition and volatilization of the ethylene compound are suppressed when the resin composition is heat-molded or heat-cured, or when a dielectric multilayer film is formed by vapor deposition, thereby enabling the optical filter to effectively block light in the ultraviolet to violet region. Furthermore, even if the optical filter is exposed to ultraviolet light during storage or manufacturing / processing (e.g., vapor deposition or mounting), deterioration of the resin components and near-infrared absorbing dye caused by the ultraviolet light can be suppressed.

[0131] The optical filter may be formed from a single or multiple resin layers, or may be formed integrally with a support. A filter integrated with a support can be formed, for example, by applying a resin composition to the surface of the support (or, if another layer such as a binder layer is present between the support and the resin layer, to the surface of the other layer) by spin coating or solvent casting, followed by drying or curing. Alternatively, a filter may be formed by thermocompression bonding a planar molded article formed from the resin composition to the support.

[0132] The resin layer formed from the resin composition may be provided on only one side of the support, or on both sides. The thickness of the resin layer is not particularly limited, but in order to ensure the desired UV protection performance, it is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, and preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. When the resin layer is formed by applying a resin composition in the form of a paint onto the support, the strength of the filter can be ensured by the support, so the thickness of the resin layer can be further reduced. When the resin layer is formed on the support, the thickness of the resin layer is, for example, preferably 50 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0133] As the support, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. The resin plate or resin film used as the support is preferably formed, for example, from the resin components described above. From the viewpoint of improving the heat resistance of the optical filter, it is preferable to use a glass substrate as the support, and the optical filter thus formed can be mounted on an electronic component, for example, by solder reflow. Furthermore, since the glass substrate is less likely to crack or warp even when exposed to high temperatures, it is easier to ensure adhesion with the resin layer. When a glass substrate is used as the support, a binder layer formed, for example, from a silane coupling agent may be provided between the support and the resin layer, thereby improving adhesion between the resin layer and the glass substrate.

[0134] The thickness of the support (substrate) is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and is preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of thinning.

[0135] A resin layer formed from a resin composition may be laminated with a second resin layer, which may be a protective layer made of the same or a different resin as that of the resin layer. By providing a protective layer, the durability (decomposition resistance) of the ethylene compound contained in the resin layer can be increased. 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 a support, the protective layer is preferably provided on the side of the resin layer opposite the support.

[0136] The optical filter may have an anti-reflection or anti-glare layer (anti-reflection film) that reduces reflections from fluorescent lights, etc., a layer with scratch resistance, a transparent substrate with other functions, etc. The optical filter may have an ultraviolet reflective film or near-infrared reflective film on the resin layer. The ultraviolet reflective film or near-infrared reflective film is preferably provided on the light incident side of the resin layer. If the optical filter has an ultraviolet reflective film or near-infrared reflective film, ultraviolet and near-infrared rays can be further blocked from the light transmitted through the optical filter. The ultraviolet reflective film and near-infrared reflective film may have both ultraviolet and near-infrared reflective functions in one film.

[0137] Ultraviolet reflective films, near-infrared reflective films, and anti-reflection films (visible light anti-reflection films) can be composed of a dielectric multilayer film in which high-refractive index material layers and low-refractive index material layers are alternately stacked. Therefore, when imparting such functions to an optical filter, it is preferable that the optical filter has a dielectric multilayer film. Materials having a refractive index of 1.7 or higher can be used as materials for the high-refractive index material layer, and materials with a refractive index ranging from 1.7 to 2.5 are typically selected. Examples of materials for the high-refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of these oxides and nitrides, and mixtures thereof doped with metals such as aluminum and copper or carbon (e.g., tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO)). Materials having a refractive index of 1.6 or lower can be used as materials for the low-refractive index material layer, and materials with a refractive index ranging from 1.2 to 1.6 are typically selected. Examples of materials that can be used to form the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

[0138] The optical filter may also have an aluminum vapor deposition film, a thin film of a noble metal, or a resin film in which metal oxide fine particles containing indium oxide as the main component and a small amount of tin oxide are dispersed.

[0139] The thickness of the optical filter is preferably, for example, 1 mm or less. This makes it possible to fully meet the demand for miniaturization of imaging elements, for example. The thickness of the optical filter is more preferably 500 μm or less, even more preferably 300 μm or less, and even more preferably 150 μm or less, and is preferably 30 μm or more, and even more preferably 50 μm or more.

[0140] Optical filters can be used as one of the components of sensors such as image sensors (imaging elements), illuminance sensors, and proximity sensors. For example, image sensors are used as electronic components that convert light from a subject into electrical signals and output the signals, and examples of such sensors include CCDs (Charge Coupled Devices) and CMOSs ​​(Complementary Metal-Oxide Semiconductors). Image sensors can be used in mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), and the like. The sensor contains one or more of the optical filters described above, and may further include other filters (for example, visible light cut filters, infrared cut filters, ultraviolet cut filters, etc.) and lenses, as necessary. [Example]

[0141] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below-described aims, and all such modifications are included in the technical scope of the present invention.

[0142] (1) Compound synthesis (1-1) Synthesis Example 1: Synthesis of ethylene compound 1 A 200 mL four-neck flask was charged with 4.98 g (0.039 mol) of 4-fluorobenzaldehyde, 3.65 g (0.020 mol) of 3,6-dioxa-1,8-octanedithiol, 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile. The mixture was reacted at 60 °C for 12 hours under nitrogen flow (10 mL / min) with stirring using a stirring blade. After completion of the reaction, the insoluble matter was filtered off under reduced pressure, and the solvent was removed using an evaporator. The resulting concentrate was placed in a 200 mL four-neck flask, to which 10.04 g (0.079 mol) of isopropyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added. The mixture was reacted under reflux for 4 hours. After the reaction was completed, the solvent was removed using an evaporator, and 300 g of methanol was added to the resulting concentrate. The target product was isolated by recrystallization while cooling to an internal temperature of 5°C, yielding 8.3 g of powdered ethylene compound 1. The yield relative to 4-fluorobenzaldehyde was 41.1 mol%. Approximately 5 mg of the resulting compound was taken and diluted with a predetermined amount of deuterated solvent (deuterated chloroform or deuterated dimethyl sulfoxide), 1 The structure was identified by H-NMR measurement.

[0143] [ka]

[0144] (1-2) Synthesis Example 2: Synthesis of ethylene compound 2 Except for using n-butyl cyanoacetate instead of isopropyl cyanoacetate in Synthesis Example 1, 7.5 g of ethylene compound 2 (powder) shown in Table 1 was obtained in the same manner as in Synthesis Example 1. The yield based on 4-fluorobenzaldehyde was 60.4 mol %.

[0145] (1-3) Synthesis Example 3: Synthesis of ethylene compound 3 Except for using tert-butyl cyanoacetate instead of isopropyl cyanoacetate in Synthesis Example 1, 5.1 g of ethylene compound 3 (powder) shown in Table 1 was obtained in the same manner as in Synthesis Example 1. The yield based on 4-fluorobenzaldehyde was 41.1 mol %.

[0146] (1-4) Synthesis Example 4: Synthesis of ethylene compound 4 The same procedure as in Synthesis Example 1 was repeated, except that 2-ethylhexyl cyanoacetate was used instead of isopropyl cyanoacetate, and the target compound was isolated by column chromatography (developing solvent: chloroform), to obtain 6.6 g of ethylene compound 4 (liquid) shown in Table 1. The yield based on 4-fluorobenzaldehyde was 45.2 mol%.

[0147] (1-5) Synthesis Example 5: Synthesis of Comparative Ethylene Compound 1 The same procedure as in Synthesis Example 1 was repeated, except that bis(2-mercaptoethyl) ether was used instead of 3,6-dioxa-1,8-octanedithiol, n-butyl cyanoacetate was used instead of isopropyl cyanoacetate, and the target product was isolated by column chromatography (developing solvent: chloroform), to obtain 1.3 g of comparative ethylene compound 1 shown in Table 1. The yield based on 4-fluorobenzaldehyde was 14.8 mol %.

[0148] (1-6) Synthesis Example 6: Synthesis of Comparative Ethylene Compound 2 The same procedure as in Synthesis Example 1 was repeated, except that bis(2-mercaptoethyl) ether was used instead of 3,6-dioxa-1,8-octanedithiol, 2-ethylhexyl cyanoacetate was used instead of isopropyl cyanoacetate, and the target product was isolated by column chromatography (developing solvent: chloroform), to obtain 2.5 g of comparative ethylene compound 2 shown in Table 1. The yield based on 4-fluorobenzaldehyde was 24.2 mol%.

[0149] (1-7) Synthesis Example 7: Synthesis of Comparative Ethylene Compound 3 The same procedure as in Synthesis Example 1 was repeated, except that methyl cyanoacetate was used instead of isopropyl cyanoacetate, and the target compound was isolated by column chromatography (developing solvent: chloroform), to obtain 3.8 g of comparative ethylene compound 3 shown in Table 1. The yield based on 4-fluorobenzaldehyde was 75.6 mol%.

[0150] (1-8) Synthesis Example 8: Synthesis of Comparative Ethylene Compound 4 The same procedure as in Synthesis Example 1 was repeated, except that isobutyl cyanoacetate was used instead of isopropyl cyanoacetate, and the target compound was isolated by column chromatography (developing solvent: chloroform), to obtain 4.6 g of comparative ethylene compound 4 shown in Table 1. The yield based on 4-fluorobenzaldehyde was 79.6 mol %.

[0151] [Table 1]

[0152] (2) Absorption spectrum measurement of ethylene compound solutions The absorption spectrum (transmission spectrum) of each toluene solution of ethylene compound was measured using a spectrophotometer (Shimadzu Corporation, UV-1800). The transmittance of light in the wavelength range of 300 nm to 1100 nm was measured at 1 nm intervals, and the maximum wavelength λmax of the maximum absorption peak in the wavelength range of 300 nm to 800 nm was determined. The results are summarized in Table 2. The absorption spectrum of the toluene solution of ethylene compound 1 is shown in Figure 1.

[0153] [Table 2]

[0154] (3) Solubility of ethylene compounds in solvents A predetermined amount of an ethylene compound was added to methyl ethyl ketone or methyl isobutyl ketone and stirred, and the resulting solution was checked for turbidity. The ethylene compound was added to each solvent to a concentration of 5 mass%, 10 mass%, 15 mass%, or 20 mass%. Ethylene Compounds 1 to 4 did not exhibit turbidity at a concentration of 20 mass% in methyl ethyl ketone. Ethylene Compound 1 did not exhibit turbidity at a concentration of 15 mass% in methyl isobutyl ketone, but did exhibit turbidity at a concentration of 20 mass%, and Ethylene Compounds 2 to 4 did not exhibit turbidity even at a concentration of 20 mass%. On the other hand, Comparative Ethylene Compounds 1 to 4 exhibited turbidity at a concentration of 5 mass% in both methyl ethyl ketone and methyl isobutyl ketone. It was found that Ethylene Compounds 1 to 4 have high solubility in organic solvents.

[0155] (4) Preparation of ethylene compound-containing epoxy resin composition (EP resin) (4-1) Preparation of cationic curing catalyst According to the synthesis method described in International Publication No. 1997 / 031924, 255 g of Isopar (registered trademark) E solution manufactured by Ando Parachemie Co., Ltd., containing 7% TPB (tris(pentafluorophenyl)borane), was prepared. Water was added dropwise to this solution at 60°C to precipitate white crystals, which were then cooled to room temperature, suction filtered, and washed with n-heptane. The resulting cake was dried under reduced pressure at 60°C to obtain 18.7 g of a white crystalline TPB-water complex (TPB-containing powder). This complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. The dry complex had a water content of 9.2% (Karl Fischer moisture meter), and a TPB content of 90.8%. 19 F-NMR and GC analyses were performed, but no peaks other than TPB were detected. 2.0 g of the resulting TPB-water complex was combined with 1.1 g of toluene and mixed at room temperature for 10 minutes. 2.6 g of a 2 mol / L ammonia-ethanol solution was then added and mixed at room temperature for 60 minutes to obtain a homogeneous solution of the TPB catalyst. This was used as the cationic curing catalyst.

[0156] (4-2) Preparation of silane hydrolyzate solution 8.0 g of 3-glycidoxypropyltrimethoxysilane (Dow Corning Toray Co., Ltd., OFS-6040), 11.4 g of 2-propanol, and 0.2 g of distilled water were combined and mixed uniformly at 25°C. 0.4 g of formic acid was added and mixed for 90 minutes to promote the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane, yielding a silane hydrolyzate solution.

[0157] (4-3) Preparation of epoxy resin composition 54.3 g of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (Daicel Corporation, EHPE3150) was used as the epoxy resin, 58.6 g of toluene and 65.0 g of 1,2,4-trimethylbenzene were used as the solvent, 4.8 g of squarylium compound A (described in Examples 1-18 of JP 2016-74649 A) ​​was used as the near-infrared absorbing dye, 4.9 g of the ethylene compound 2 obtained in Synthesis Example 2, and 0.2 g of BYK-306 (polyether-modified polydimethylsiloxane) manufactured by BYK-Chemie was used as the surface conditioner, and the mixture was mixed uniformly at 40°C. The resulting mixture was then cooled to 25°C, and 5.4 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), 1.4 g of the cationic curing catalyst obtained above, and 5.4 g of the silane hydrolyzate solution were added and mixed uniformly. This was filtered through a filter with a pore size of 0.45 μm (manufactured by GL Science, non-aqueous 13N) to remove foreign matter, thereby obtaining an epoxy resin composition.

[0158] [ka]

[0159] (5) Preparation of ethylene compound-containing polyarylate resin (PAR resin) composition (5-1) Synthesis of polyarylate resin A 2-liter reactor equipped with a stirring blade was charged with 10.01 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.59 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water. After dissolving, 0.89 g (0.009 mol) of triethylamine was added and dissolved. A solution of 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride dissolved in 500 g of methylene chloride was placed in a dropping funnel and attached to the reactor. The solution in the reactor was stirred while maintaining the temperature at 20°C, and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. A solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was then added and stirred for 60 minutes. The resulting reaction solution was neutralized by adding an aqueous solution of acetic acid to adjust the pH of the aqueous phase to 7, and then the oil and aqueous phases were separated using a separatory funnel. The resulting oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80°C to obtain a white solid polyarylate resin. The yield was 11.5 g. The weight-average molecular weight (Mw) of the resulting 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 were determined by gel permeation chromatography and expressed in terms of polystyrene.

[0160] (5-2) Preparation of polyarylate resin composition 1 19.7 g of the polyarylate resin obtained above was added to a mixed solvent of 69.1 g of toluene and 104.6 g of o-xylene, and then 1.2 g of the squarylium compound A and 0.5 g of the squarylium compound B shown below as near-infrared absorbing pigments, 2.2 g of the ethylene compound 2 obtained in Synthesis Example 2, 0.1 g of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK-Chemie as a surface conditioner, 0.6 g of pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), and 2.0 g of the silane hydrolyzate solution obtained in (4-2) were added and mixed uniformly. This was filtered through a 0.1 μm pore size filter (GL Science, non-aqueous 13N) to remove foreign matter, and polyarylate resin composition 1 was obtained.

[0161] [ka]

[0162] (5-3) Preparation of polyarylate resin composition 2 Polyarylate resin composition 2 was obtained in the same manner as in preparation of polyarylate resin composition 1, except that in preparation of polyarylate resin composition 1, toluene was changed to 55.3 g and 1,2,4-trimethylbenzene was used in place of o-xylene.

[0163] (6) Preparation of optical filters Each resin composition obtained above was dispensed in an amount of 2 cc onto a glass substrate (Schott, D263Teco). A spin coater (Mikasa, 1H-D7) was used to spin the substrate at 1900 rpm over 0.2 seconds, maintain that speed for 20 seconds, and then reduce the speed to 0 rpm over 0.2 seconds to form a film of the resin composition on the glass substrate. The glass substrate with the resin composition film was initially dried at 100°C for 3 minutes in a precision incubator (Yamato Scientific, DH611) (before curing). The atmosphere was then purged with nitrogen at 50°C for 30 minutes in an inert oven (Yamato Scientific, DN610I), after which the temperature was raised to 190°C over approximately 15 minutes and the substrate was dried at 190°C for 30 minutes to 1 hour in a nitrogen atmosphere to form a resin layer (absorption layer) on the glass substrate (after curing). The resin layer formed on the glass substrate was 2 μm thick. The thickness of the resin layer was determined by measuring the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone with a micrometer, and then calculating the difference between the two.

[0164] (7) Measurement of transmission (absorption) spectrum of optical filters (7-1) Measurement of transmission spectrum of optical filters For each optical filter with a resin layer formed on a glass substrate, the transmission spectrum was measured at a measurement interval of 1 nm using a spectrophotometer (Shimadzu Corporation, UV-1800) to determine the transmittance of light with wavelengths of 300 nm to 800 nm. The transmission spectra were measured for the optical filters before and after curing the resin layer. The results are shown in Figures 2 to 4.

[0165] (7-2) Evaluation As shown in Figures 2, 3, and 4, the transmission spectrum of the optical filter formed from the resin composition containing the ethylene compound did not change significantly before and after curing at 190°C. These results demonstrate that the ethylene compound of the present invention has excellent heat resistance. Furthermore, no turbidity or bleeding out of the cured resin was observed in the obtained optical filter. [Industrial Applicability]

[0166] The ethylene compound of the present invention can be used as an ultraviolet absorber, or by blending it with a resin and forming it into a film or the like, it can be used as a light selective transmission filter that is useful for applications such as optical devices, display devices, mechanical parts, and electric / electronic parts.

Claims

1. An ethylene compound represented by the following formula (1): 【Chemistry 1】 [In formula (1), L represents an alkylene group, —O—, —S—, —SO—, a methine group (—C<) which may have an alkyl group, a tetravalent linking group of >C<, or a linking group formed by combining these; a represents an integer of 2 or more; Each A independently represents a group represented by the following formula (2): Multiple groups A are linked to each other via a linking group L via 7 or more atoms. 【Chemistry 2】 [In formula (2), R １ represents a linear alkyl group having 4 or more carbon atoms, a branched alkyl group having 3 or more carbon atoms branched at the α-position carbon, or a branched alkyl group having 7 or more carbon atoms branched at a carbon other than the α-position, R ２ represents a hydrogen atom or an alkyl group, R ３ represents a hydrogen atom, an organic group, or a polar functional group, and a plurality of R ３ may be the same or different from each other, X represents a sulfur atom or an oxygen atom; * represents the bonding site with the linking group L in formula (1).

2. 2. The ethylene compound according to claim 1, which has a maximum absorption peak at a wavelength of 340 nm or more and 400 nm or less in an absorption spectrum measured in toluene over a wavelength range of 300 nm to 600 nm.

3. An ultraviolet absorber comprising the ethylene compound according to claim 1 or 2.

4. An ethylene compound solution comprising the ethylene compound according to claim 1 or 2 and a solvent.

5. A resin composition comprising the ethylene compound according to claim 1 or 2 and a resin component.

6. The resin composition according to claim 5, further comprising a near-infrared absorbing dye and / or a visible light absorbing dye.

7. A cured product obtained by curing the resin composition according to claim 5 or 6.

8. An optical filter comprising the resin composition according to claim 5 or 6.

9. A sensor comprising the optical filter according to claim 8.

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