Compound, curable resin composition, cured product and optical element

Abstract

To provide: a compound that yields a cured product with a high refractive index, a low Abbe number, and a high transmittance; a curable resin composition containing the compound; a cured product of the curable resin composition; and an optical element having the cured product.SOLUTION: The present invention provides a compound represented by the formula 1. X1, X2: an optionally substituted naphthyl group. Y: -C(CH3)2-, -CH2-, -S-, or -SO2-. Z1, Z2: a polymerizable group. Q1, Q2: a C1-12 divalent linking group. n1, n2: an integer of 1-4. m1, m2: an integer of 0-3.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, a curable resin composition, a cured product, and an optical element. [Background technology]

[0002] The refractive index of a lens is wavelength dependent, so if the wavelength of a light ray differs, the focal length of the lens also differs. This relationship causes chromatic aberration. In lenses used in imaging systems, chromatic aberration is corrected by combining lenses with high Abbe numbers and lenses with low Abbe numbers.

[0003] In terms of making lenses thinner, lenses with a high refractive index are more suitable. Also, resin lenses have the advantage of being easier to process than glass lenses. For these reasons, monomers have been developed to obtain cured products with high refractive indexes and low Abbe numbers.

[0004] Fluorene derivatives incorporating naphthalene are well known as monomers that can produce cured products with high refractive index and low Abbe number. However, since fluorene has a long conjugation length, the absorption wavelengths may increase, resulting in a risk of reduced transmittance. On the other hand, since the conjugation system between aromatic rings is cut off in bisphenol derivatives, it is expected that the absorption wavelengths will not increase (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-231704 A [Patent Document 2] Japanese Patent Application Publication No. 4-202308 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the bisphenol derivatives described in Patent Documents 1 and 2 do not provide a cured product having a high refractive index, a low Abbe number, and a high transmittance.

[0007] The present invention provides a compound that can give a cured product that has a high refractive index, a low Abbe number, and a high transmittance; a curable resin composition containing the compound; a cured product of the curable resin composition; and an optical element having the cured product. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A compound represented by the following formula 1. [ka] In formula 1, X 1 and X 2 is a naphthyl group which may have a substituent, Y is -C(CH3)2-, -CH2-, -S-, or -SO2-; Z 1 and Z 2 is a polymerizable group, Q 1 and Q 2 is a divalent linking group having 1 to 12 carbon atoms, n1 and n2 are integers from 1 to 4, m1 and m2 are integers of 0 to 3, X 1 and X 2 may be the same or different, Z 1 and Z 2 may be the same or different, Q 1 and Q 2 may be the same or different, n1 and n2 may be the same or different; m1 and m2 may be the same or different. [2] The compound according to [1], represented by the following formula 11: [ka] In formula 11, X 11 , X 12 , X 21 and X 22 is a naphthyl group which may have a substituent, X 11 , X 12 , X 21 and X 22 may be the same or different. [3]Q 1 and Q 2 wherein either or both of the above are an oxyalkylene group having 1 to 3 carbon atoms. [4] Z 1 and Z 2 The compound according to any one of [1] to [3], wherein either or both of the following are photocurable functional groups: [5] The compound according to any one of [1] to [4], wherein the absorption edge of a spectral transmittance curve determined by ultraviolet-visible spectroscopy is 380 nm or less. [6] The compound according to any one of [1] to [5], which has a refractive index of 1.65 to 1.75 at 30° C. for d-line having a wavelength of 587 nm and an Abbe number of 20 or less. [7] A curable resin composition comprising the compound according to any one of [1] to [6]. [8] A cured product of the curable resin composition according to [7]. [9] An optical element comprising the cured product according to [8].

[10] The optical element according to [9], which is a lens. Effect of the Invention

[0009] The compound of the present invention gives a cured product having a low Abbe number, high transmittance, and high refractive index. According to the curable resin composition of the present invention, a lens having a low Abbe number, high transmittance, and high refractive index can be obtained. The cured product of the present invention has a low Abbe number, high transmittance, and high refractive index. The optical element of the present invention has a cured product that has a low Abbe number, high transmittance, and high refractive index. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a plan view diagrammatically illustrating a method for preparing a test sample used in measuring the Abbe number and the refractive index in the examples. [Diagram 2] FIG. 2 is a cross-sectional view that typically illustrates a method for preparing a test sample used in measuring the Abbe number and the refractive index in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The meaning of the terms is as follows: The term "etheric oxygen atom" refers to an oxygen atom which forms an ether bond (-O-) between carbon atoms. The term "(meth)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. "(Meth)acrylate" is a general term for acrylate and methacrylate. The "absorption edge" is determined by the method described in the Examples. The "refractive index" is determined by the method described in the Examples. The "Abbe number" is determined by the method described in the Examples. The symbol "to" indicating a numerical range means that the numerical values ​​before and after the symbol "to" are included as the lower and upper limits. The numerical ranges disclosed in this specification can be combined in any manner to form new numerical ranges. The compound represented by formula A may be referred to as "Compound A." The same applies to compounds represented by other formulas.

[0012] [Compound] One aspect of the present invention relates to a compound represented by the following formula 1 (hereinafter referred to as "the compound").

[0013] [ka]

[0014] In formula 1, X 1 and X 2 is a naphthyl group which may have a substituent. 1 and X 2 may be the same or different. The naphthyl group may be a 1-naphthyl group or a 2-naphthyl group. Examples of the substituent that the naphthyl group may have include an alkyl group having 1 to 12 carbon atoms, an aryl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a sulfo group, a sulfide group, an amido group, a hydroxy group, and an amino group. The naphthyl group may have one or more kinds of substituents. The naphthyl group may further have another substituent.

[0015] The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-decyl. Examples of branched alkyl groups include isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, and 2-ethylhexyl. Examples of cyclic alkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0016] Examples of the aryl group having 3 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-imidazolyl group, a 2-pyridyl group, a 2-furyl group, a 9-carbazoyl group, and a 2-thienyl group.

[0017] Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, and a trifluoromethoxy group.

[0018] The acyl group having 1 to 12 carbon atoms may be an aliphatic acyl group or an aromatic acyl group. Examples of the aliphatic acyl group include a formyl group, an acetyl group, a propionyl group, a 2-methylpropionyl group, a 2,2-dimethylpropionyl group, and a 2-ethylhexanoyl group. Examples of the aromatic acyl group include a benzoyl group, a 1-naphthylcarbonyl group, a 2-naphthylcarbonyl group, and a 2-furylcarbonyl group.

[0019] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0020] In formula 1, n1 and n2 are integers of 1 to 4. In the present compound, n1 and n2 may be the same or different. n1 and n2 are preferably 1 to 3, more preferably 1 or 2, and most preferably 2. When n1 and n2 are equal to or greater than the lower limit of the above-mentioned numerical range, the effect of improving the refractive index by introducing a naphthyl group is easily obtained. When n1 and n2 are equal to or less than the upper limit of the above-mentioned numerical range, the present compound is easily synthesized.

[0021] In formula 1, Y is -C(CH3)2-, -CH2-, -S-, or -SO2-.

[0022] In equation 1, Q 1 and Q 2 is a divalent linking group having 1 to 12 carbon atoms. 1 and Q 2 may be the same or different. Examples of the divalent linking group include an alkylene group having 1 to 12 carbon atoms and an oxyalkylene group having 1 to 12 carbon atoms. In terms of solubility, an oxyalkylene group having 1 to 6 carbon atoms is preferred.

[0023] When the carbon number of the alkylene group or the carbon number of the oxyalkylene group is 2 or more, the alkylene group or the oxyalkylene group may have an etheric oxygen atom between the carbon atoms. The alkylene group or the oxyalkylene group may be linear or may have a branched structure.

[0024] The divalent linking group may have a heteroatom, for example, a nitrogen atom or a sulfur atom.

[0025] Q 1 and Q 2 Examples of the divalent linking group include -OCH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2CH2-, -OCH2CH2CH2CH2-, -CH2-, -CH2OCH2CH2-, -OCONHCH2CH2-, -OCONHCH2CH2OCH2CH2-, -SO-, -SO2-, -SCH2-, -SCONHCH2CH2-, -COOCH2CH2-, -COSCH2CH2-, -NHCOOCH2CH2-, -NHCO-, and -CH2NHCOCH2CH2-.

[0026] In formula 1, m1 and m2 are integers of 0 to 3. In the present compound, m1 and m2 may be the same or different. Each of m1 and m2 is preferably 1 to 3, more preferably 1 or 2, and most preferably 1. When m1 and m2 are each within the above numerical range, the effect of improving the refractive index is easily obtained.

[0027] In equation 1, Z 1 and Z 2 is a polymerizable group. 1 and Z 2 may be the same or different. The polymerizable group may be a photocurable functional group or a thermosetting functional group, and is not particularly limited.

[0028] Examples of the photocurable functional group include a (meth)acryloyl group, an epoxy group, a glycidyl group, an allyl group, a vinyl group, and a thiol group. Among these, a (meth)acryloyl group, an epoxy group, and a glycidyl group are preferred, a (meth)acryloyl group and an epoxy group are more preferred, and a (meth)acryloyl group is even more preferred.

[0029] Examples of the thermosetting functional group include an epoxy group, a glycidyl group, an isocyanate group, a hydroxy group, a carboxyl group, and an amide group. Among these, an epoxy group, a glycidyl group, a hydroxy group, and an isocyanate group are preferred, an epoxy group and a glycidyl group are more preferred, and an epoxy group is even more preferred.

[0030] In formula 1, X 1 is bonded to at least one carbon atom selected from the group consisting of the carbon atom at substitution position number 1, the carbon atom at substitution position number 2, the carbon atom at substitution position number 3, and the carbon atom at substitution position number 4. Similarly, X 2 is bonded to at least one carbon atom selected from the group consisting of the carbon atom at substitution position number 5, the carbon atom at substitution position number 6, the carbon atom at substitution position number 7, and the carbon atom at substitution position number 8.

[0031] In formula 1, X 1 is preferably bonded to the carbon atom at substitution position number 2 or the carbon atom at substitution position number 3. When n1 is 2 or more, X is preferably bonded to at least the carbon atom at substitution position number 2 and the carbon atom at substitution position number 3. 1 is more preferably bonded.

[0032] In formula 1, X 2 is preferably bonded to the carbon atom at substitution position number 6 or the carbon atom at substitution position number 7. When n2 is 2 or more, X is preferably bonded to at least the carbon atom at substitution position number 6 and the carbon atom at substitution position number 7. 2 is more preferably bonded.

[0033] A preferred embodiment of the present compound relates to a compound represented by the following formula 11. [ka]

[0034] In formula 11, X 11 , X 12 , X 21 and X 22 is a naphthyl group which may have a substituent; X11 , X 12 , X 21 and X 22 Y and Z may be the same or different. 1 and Z 2 , Q 1 and Q 2 , m1 and m2 are the same as in Formula 1. X 11 , X 12 , X 21 and X 22 For more information, see X 1 and X 2 This is the same as that explained for

[0035] The absorption edge of the spectral transmittance curve obtained by ultraviolet-visible spectroscopy is preferably 380 nm or less, more preferably 370 nm or less, even more preferably 360 nm or less, particularly preferably 350 nm or less, and most preferably 340 nm or less. If the absorption edge of the absorption spectrum is below the upper limit, it is easy to obtain a cured product with high transmittance. The lower limit of the absorption edge of the absorption spectrum is not particularly limited, but may be, for example, 300 nm.

[0036] A cured product can be obtained with a compound according to a preferred embodiment, which has a refractive index of 1.65 to 1.75 at 30°C when exposed to d-line having a wavelength of 587 nm, and an Abbe number of 20 or less. The refractive index is preferably 1.65 to 1.75, more preferably 1.66 to 1.74, and even more preferably 1.68 to 1.72. The Abbe number is preferably 20 or less, more preferably 18 or less, and even more preferably 15 or less.

[0037] The method for synthesizing the present compound is not particularly limited. The present compound can be synthesized by appropriately combining various synthetic reactions, utilizing the characteristics based on the basic structure and the types of substituents.

[0038] The solvent used in the synthesis may be appropriately selected within a range that does not adversely affect the reaction, such as dimethylformamide, dichloromethane, tetrahydrofuran, halogenated hydrocarbons (dichloromethane, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), aromatic hydrocarbons (benzene, toluene, etc.), aliphatic hydrocarbons (hexane, pentane, etc.), and amide solvents (N,N-dimethylformamide, N-methylpyrrolidone, etc.). The solvent used in the synthesis may be one type alone or two or more types in combination.

[0039] (Mechanism of action) The compound described above has a bisphenol skeleton, so that the absorption is unlikely to shift to longer wavelengths. Therefore, a cured product with high transmittance can be obtained. In addition, since a naphthyl group is introduced into the bisphenol skeleton of the compound, a cured product with a high refractive index and a low Abbe number can be obtained.

[0040] [Curable resin composition] Another aspect of the present invention relates to a curable resin composition. The curable resin composition contains the above-mentioned present compound. The curable resin composition preferably further contains an initiator. The initiator is not particularly limited as long as it initiates the curing of the curable resin composition. The initiator may be used alone or in combination of two or more kinds.

[0041] When the polymerizable group of the present compound is a photocurable functional group, the curable resin composition preferably further contains a photopolymerization initiator. The photopolymerization initiator generates radicals by absorbing light. As the photopolymerization initiator, a photoradical polymerization initiator is preferable from the viewpoint of ease of production of a cured product. Examples of the photoradical polymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, oxime ester-based photopolymerization initiators, oxyphenylacetic acid ester-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, benzyl-(o-ethoxycarbonyl)-α-monoxime, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and tert-butyl peroxypivalate. In terms of sensitivity and compatibility, alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, benzoin-based photopolymerization initiators, and benzophenone-based photopolymerization initiators are preferred. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0042] When the polymerizable group of the present compound is a photocurable functional group, the curable resin composition preferably further contains an ultraviolet cationic polymerization initiator. The ultraviolet cationic polymerization initiator generates an acid capable of cationic polymerization by irradiation with ultraviolet rays. Examples of the ultraviolet cationic polymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromine salt compounds. The anion component of the UV cationic polymerization initiator is, for example, SbF6 - , PF6 - , BF4 - , AsF6 - , B(C6F5)4 - Examples include:

[0043] As an ultraviolet cationic polymerization initiator, B(C6F5)4 is used as the anion component from the viewpoints of curability and transparency of the cured product. - , PF6 - or SbF6 -Onium salts such as aromatic sulfonium salts having the anion component B(C6F5)4 are preferred. - More preferred is an onium salt such as an aromatic sulfonium salt having the following formula: The ultraviolet cationic polymerization initiator may be used alone or in combination of two or more kinds.

[0044] When the polymerizable group of the present compound is a thermosetting functional group, the curable resin composition preferably further contains a thermal cationic polymerization initiator. The thermal cationic polymerization initiator is a compound that generates an acid by heat treatment and initiates the curing reaction of the cationic curable compound contained in the curable resin composition. The thermal cationic polymerization initiator is composed of a cationic part that absorbs heat and an anionic part that serves as a source of acid generation. The thermal cationic polymerization initiator may be used alone or in combination of two or more kinds. Examples of the thermal cationic polymerization initiator include iodonium salt compounds and sulfonium salt compounds.

[0045] Examples of the cationic moiety of the thermal cationic polymerization initiator include monoarylsulfonium ions such as 4-hydroxyphenyl-methyl-benzylsulfonium ion, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonium ion, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium ion, and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium ion. The anion moiety of the thermal cationic polymerization initiator may be the same as the anion moiety of the ultraviolet cationic polymerization initiator.

[0046] The curable resin composition may further contain a solvent as necessary. The solvent is not particularly limited as long as it is a compound capable of dissolving the present compound. Examples of the solvent include dichloromethane, toluene, dimethylformamide, tetrahydrofuran, and cyclohexanone.

[0047] The curable resin composition may further contain compounds other than the present compound that become resin components upon curing, so long as the effects of the present invention are not impaired. The other compounds are not particularly limited, but include, for example, oxetane compounds, vinyl compounds, and epoxy compounds.

[0048] Examples of the oxetane compound include various monofunctional oxetane compounds and polyfunctional oxetane compounds. Examples of the monofunctional oxetane compound include, but are not limited to, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane. Examples of the polyfunctional oxetane compound include, but are not limited to, 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane.

[0049] Examples of the vinyl compound include, but are not limited to, various monofunctional (meth)acrylates and polyfunctional (meth)acrylates. Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, paracumylphenol ethylene oxide modified (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and isobornyl acrylate. Examples of polyfunctional (meth)acrylates include (meth)acrylates having two (meth)acryloyl groups, such as bisphenol F ethylene oxide modified di(meth)acrylate, bisphenol Z ethylene oxide modified di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; Examples of the (meth)acrylate include (meth)acrylates having three (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, and trimethylolpropane ethylene oxide modified tri(meth)acrylate. In addition to these, (meth)acrylates having four or more (meth)acryloyl groups can also be used. Oligomers such as polyester (meth)acrylate, urethane (meth)acrylate, and epoxy (meth)acrylate can also be used. Examples of epoxy (meth)acrylates include (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Examples of the epoxy resin include (meth)acrylates of epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins.

[0050] An example of the epoxy compound is 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, but is not particularly limited thereto.

[0051] The curable resin composition may further contain optional additives as necessary, such as coupling agents (silane-based coupling agents, titanium-based coupling agents, etc.), flexibility-imparting agents (synthetic rubbers, polyorganosiloxanes, etc.), antioxidants, defoamers, hydrocarbon waxes, and inorganic fillers.

[0052] The total mass of the resin components in the curable resin composition is, in principle, the content of the present compound in the curable resin composition. The content of the initiator is not included in the total mass of the resin components. When the curable resin composition further contains, in addition to the present compound, other compounds that become resin components upon curing, the content of the other compounds is included in the total mass of the resin components.

[0053] The content of the present compound in the curable resin composition is preferably 10 to 100 mass %, more preferably 30 to 100 mass %, and even more preferably 40 to 100 mass % of the total mass of the resin components in the curable resin composition. When the content of the present compound is equal to or more than the lower limit of the above numerical range, a cured product having a low Abbe number, a high transmittance, and a high refractive index is easily obtained.

[0054] When the curable resin composition further contains other compounds that become resin components by curing in addition to the compound, the content of the other compounds is preferably 1 to 90 mass %, more preferably 1 to 70 mass %, and even more preferably 1 to 60 mass % of the total mass of the resin components in the curable resin composition. If the content of the other compounds is equal to or greater than the lower limit of the above numerical range, the properties of the other compounds are easily imparted to the cured product. If the content of the other compounds is equal to or less than the upper limit of the above numerical range, a cured product having a low Abbe number, a high transmittance, and a high refractive index is easily obtained.

[0055] The content of the initiator in the curable resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3.0 parts by mass, based on 100 parts by mass of the total mass of the resin components in the curable resin composition. When the content of the initiator is equal to or greater than the lower limit of the above-mentioned numerical range, the curing property is excellent. When the content of the initiator is equal to or less than the upper limit of the above-mentioned numerical range, coloration of the cured product is easily suppressed.

[0056] The curable resin composition can be prepared by mixing the present compound with an initiator. If necessary, other compounds or additives that become resin components upon curing may be further blended into the curable resin composition.

[0057] [Application] The curable resin composition can be irradiated with light, heated, or the like depending on the type of initiator to produce a cured product. The use of the cured product of the curable resin composition is not particularly limited. For example, optical elements such as lenses, prisms, reflecting mirrors, filters, and diffraction gratings are preferred.

[0058] The shape and outer diameter of the cured product are not particularly limited and can be appropriately set depending on the application. The thickness of the cured product is also not particularly limited and can be appropriately set depending on the application. EXAMPLES

[0059] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following description. Example 1 is an example, and Examples 2 and 3 are comparative examples.

[0060] [Example 1] In Example 1, the following compound A was synthesized.

[0061] [ka]

[0062] The synthesis method of compound A is as follows. First, the chemical reaction shown in the following formula E1 was carried out. Tetrabromobisphenol A bis(2-hydroxyethyl)ether (12 g, 0.01898 mol), 2-naphthaleneboronic acid (26.4 g, 0.1535 mol), palladium(II) acetate (0.36 g, 1.60 mmol), dicyclohexyl(2',6'-diisopropoxy-[1,1'-biphenyl]-2-yl)phosphine (1.44 g, 3.1 mmol), and tripotassium phosphate (44.4 g, 0.21 mol) were dissolved in a mixed solvent of toluene (86.4 mL) and water (8.4 mL). Then, the mixture was stirred overnight at 100°C under a nitrogen atmosphere. After the reaction was completed, water was added and celite filtration was performed to recover the organic layer. Next, the reaction product remaining in the aqueous layer was extracted using dichloromethane (DCM). The solvent was removed and a white solid, tetranaphthyl bisphenol A bis(2-hydroxyethyl) ether (13.4 g, 0.01632 mol), was isolated by flash column chromatography (DCM / ethyl acetate=100 / 1).

[0063] [ka]

[0064] Next, the reaction shown in formula E2 below was carried out. Tetranaphthyl bisphenol A bis(2-hydroxyethyl)ether (13.4g, 0.01632mol) was dissolved in DCM (163mL) and triethylamine (4.95g, 0.04896mol) was added. Acryloyl chloride (3.2g, 0.03590mol) was added dropwise at 0℃ under a nitrogen atmosphere. After the dropwise addition, the mixture was stirred at 0℃ for 1.5 hours and then filtered through Celite. The filtrate was washed twice with water and once with saturated saline, and the solvent was removed. Compound A (13.2g, 0.01420mol) was isolated as a white solid by flash column chromatography (DCM / hexane solution = 2 / 1). NMR spectrum of compound A: 1 H-NMR (400MHz, solvent CDCl3, standard: TMS) δ (ppm): 8.04 (s, 4H), 7.88-7.80 (m, 16H), 7.49-7.44 (m, 12) H),5.90-5.81(dd,2H),5.40-5.36(m,4H),3.43-3.45(t,4H),3.74-3.76(t,4H),1.54(s,6H)

[0065] [ka]

[0066] [Example 2] In Example 2, the following compound B was synthesized.

[0067] [ka]

[0068] The method for synthesizing compound B is as follows: First, 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-di(2-naphthyl)fluorene was synthesized with reference to the description in paragraphs 0196-0198 of the specification of Japanese Patent No. 7117932. Next, the reaction shown in the following formula E3 was carried out. 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-di(2-naphthyl)fluorene (8.2 g, 0.01187 mol) was dissolved in DCM (404 mL), and triethylamine (3.7 g, 0.03561 mol) was added. Acryloyl chloride (2.69 g, 0.02968 mol) was added dropwise at 0°C under a nitrogen atmosphere. After the dropwise addition, the mixture was stirred at 0°C for 1.5 hours, and then filtered through Celite. The filtrate was washed twice with water and once with saturated saline, and the solvent was removed. Compound B (8.6 g, 0.01068 mol) was isolated as a white solid by flash column chromatography (DCM). Compound B is a different compound from BPDN2 described in Japanese Patent No. 7117932. NMR spectrum of compound B: 1 H-NMR (400MHz, solvent CDCl3, standard: TMS) δ (ppm): 8.01 (s, 2H), 7.90-7.87 (m, 8H), 7.76-7.69 (m, 6H), 7.52-7.43 (m, 4H) 7.28-7.25 (d,4H),6.83-6.81(d,4H),6.41-6.36(d,2H),6.15-6.05(dd,2H),5.80-5.77(d,2H),4.47-4.45(t,4H),4.17-4.14(t,4H)

[0069] [ka]

[0070] [Example 3] In Example 3, the following compound C was synthesized.

[0071] [ka]

[0072] The synthesis method of compound C is as follows. First, the reaction shown in the following formula E4 was carried out. Tetrabromobisphenol A bis(2-hydroxyethyl)ether (12 g, 0.01898 mol), phenylboronic acid (18.5 g, 0.1517 mol), tetrakis(triphenylphosphine)palladium(0) (2.2 g, 1.90 mmol), potassium carbonate (62.9 g, 0.455 mol) were dissolved in a mixed solvent of toluene (234.4 mL) and water (99.7 mL), and ethanol (49.8 mL). Then, the mixture was stirred overnight at 120° C. under a nitrogen atmosphere. After the reaction was completed, the toluene and aqueous layers were separated, and the reaction product of the aqueous layer was extracted with ethyl acetate. The solvent was removed, and white solid tetraphenylbisphenol A bis(2-hydroxyethyl)ether (8.24 g, 0.013286 mol) was isolated by flash column chromatography (hexane / ethyl acetate=2 / 1).

[0073] [ka]

[0074] Next, the reaction shown in the following formula E5 was carried out. Tetraphenylbisphenol A bis(2-hydroxyethyl)ether (3.4 g, 5.44 mmol) was dissolved in DCM (78 mL), and triethylamine (1.65 g, 16.3 mmol) was added. Under a nitrogen atmosphere, acryloyl chloride (1.1 g, 12.0 mmol) was added dropwise at 0°C. After the dropwise addition was completed, the mixture was stirred at 0°C for 2 hours, and then water was added to terminate the reaction. The reactant was extracted using DCM, and the solvent was removed. Compound C (3.12 g, 4.30 mmol) was isolated as a white solid by flash column chromatography (hexane / ethyl acetate = 4 / 1).

[0075] [ka]

[0076] [Abbe number, refractive index] (1) Preparation of Curable Resin Composition The compound synthesized in each example was mixed with POB-A (a product of Kyoeisha Chemical Co., Ltd.) as a monofunctional acrylate monomer. Three types of curable resin compositions were prepared, each containing 10 mass%, 20 mass%, and 40 mass% of the compound synthesized in each example. 3 mass parts of Irgacure 184 (a product of BASF Japan Ltd.) were added as an initiator to 100 mass parts of each curable resin composition.

[0077] (2) Preparation of test samples 1 and 2 show the procedure for preparing the test sample. A first glass substrate 5 with a release treatment, two spacer glasses (thickness 0.5 mm) with a release treatment, and a second glass substrate 8 with a release treatment were prepared. The two spacer glasses 6 and 6 were arranged parallel to each other on the first glass substrate 5 so that the distance between the two spacer glasses 6 and 6 was 30 mm or more. The two spacer glasses 6 and 6 were arranged so that the thickness direction of the spacer glasses 6 and 6 was normal to the main surface of the first glass substrate 5. Then, about 0.3 g of the curable resin composition was dropped onto the main surface of the first glass substrate 5 between the two spacer glasses 6 and 6 without generating air bubbles. At this time, the amount of the curable resin composition dropped was adjusted so that the diameter R of the curable resin composition 7 in a plan view when the second glass substrate 8 was placed so as to face the first glass substrate 5 and sandwiched therebetween exceeded 30 mm (FIGS. 1 and 2). Next, a second glass substrate 8 was placed opposite the first glass substrate 5, and the curable resin composition 7 was sandwiched between them. The sandwiched curable resin composition 7 was exposed to ultraviolet light at a dose of 4500 mJ / cm using an LED lamp with a wavelength of 365 nm. 2 After irradiating the resin with UV light, the resin was cured by heating on a hot plate at 120° C. for 15 minutes. Thereafter, the film-like cured product (diameter: about 30 mm×thickness: 0.5 mm) was released from the first glass substrate 5, the two spacer glasses 6, 6, and the second glass substrate 8 to obtain a test sample.

[0078] (3) Estimation of refractive index and Abbe number First, a Metricon prism coupler (model 2010) was used to measure the refractive index of the test sample at each wavelength at 30° C. using lasers with wavelengths of 451 nm, 532 nm, 633 nm, and 932 nm. These measured values ​​were substituted into Cauchy's dispersion formula to derive an approximation formula and calculate the refractive index. Next, from the calculated results of the refractive index at each wavelength, the content of each compound in each example was plotted on the horizontal axis and the refractive index on the vertical axis to create a calibration curve. The value of 100% by mass was substituted on the horizontal axis in the calibration curve to determine the value when the content of each compound in each example was 100% by mass. The results are shown in Table 1.

[0079] (4) Calculation of Abbe number First, using a Metricon prism coupler (model 2010), the refractive index of the test sample at each wavelength was measured at 30°C using lasers with wavelengths of 451 nm, 532 nm, 633 nm, and 932 nm. These measured values ​​were substituted into Cauchy's dispersion formula to derive an approximation formula and calculate the refractive index. The Abbe number was calculated using the following formula E6. The results are shown in Table 1.

[0080] ν D =(n D -1) / (n F -n C )...Formula E6 In formula E6, ν D is the Abbe number. D is the refractive index for light with a wavelength of 589 nm. F is the refractive index for light with a wavelength of 486 nm. C is the refractive index for light with a wavelength of 656 nm.

[0081] [Absorption edge] Each compound was dissolved in acetonitrile to a concentration of 1.1 μg / mL. The acetonitrile solution of each compound was measured for its spectral transmittance curve using a UV-Visible spectrophotometer (Hitachi High-Technologies product, UV-Visible spectrophotometer U-3310). The wavelength at which the absorption coefficient becomes 0 when the absorbance at the maximum absorption wavelength λmax is set to 1 was defined as the absorption edge. The results are shown in Table 1.

[0082] [Table 1]

[0083] As shown in Table 1, in Example 1, the absorption edge was 330 nm and the transmittance was high. In addition, the refractive index was high and the Abbe number was low. In Example 1, a cured product with a high refractive index, a low Abbe number, and a high transmittance was obtained. In contrast, the absorption edge was 390 nm, close to the visible range, and the transmittance was insufficient in Example 2. The refractive index was low and the Abbe number was high in Example 3. Thus, in Examples 2 and 3, a cured product with a high refractive index, low Abbe number, and high transmittance was not obtained. [Industrial Applicability]

[0084] The compound of the present invention gives a cured product having a low Abbe number, high transmittance, and high refractive index. According to the curable resin composition of the present invention, a lens having a low Abbe number, high transmittance, and high refractive index can be obtained. The cured product of the present invention has a low Abbe number, high transmittance, and high refractive index. The optical element of the present invention has a cured product that has a low Abbe number, high transmittance, and high refractive index. [Explanation of symbols]

[0085] 5 First Glass Substrate 6 Spacer Glass 7 Curable resin composition 8 Second Glass Substrate

Claims

1. A compound represented by the following formula 1. 【Chemistry 1】 In formula 1, X １ and X ２ is a naphthyl group which may have a substituent, Y is -C(CH ３ ) ２ --, --CH ２ -, -S-, or -SO ２ - and Z １ and Z ２ is a polymerizable group, Q １ and Q. ２ is a divalent linking group having 1 to 12 carbon atoms, n １ and n ２ is an integer from 1 to 4, m １ and m ２ is an integer from 0 to 3, X １ and X ２ may be the same or different, Z １ and Z ２ may be the same or different, Q １ and Q. ２ may be the same or different, n １ and n ２ may be the same or different, m １ and m ２ may be the same or different.

2. The compound according to claim 1 , represented by the following formula 11: 【Chemistry 2】 In formula 11, X １１ , X １２ , X ２１ and X ２２ is a naphthyl group which may have a substituent, X １１ , X １２ , X ２１ and X ２２ may be the same or different.

3. Q １ and Q. ２ The compound according to claim 1, wherein either or both of the following is an oxyalkylene group having 1 to 3 carbon atoms:

4. Z １ and Z ２ The compound according to claim 1 , wherein either or both of the following is a photocurable functional group:

5. The compound according to claim 1, having an absorption edge of a spectral transmittance curve determined by ultraviolet-visible spectroscopy at 380 nm or less.

6. The compound according to claim 1, having a refractive index of 1.65 to 1.75 at 30° C. for d-line having a wavelength of 587 nm, and an Abbe number of 20 or less.

7. A curable resin composition comprising the compound according to any one of claims 1 to 6.

8. A cured product of the curable resin composition according to claim 7.

9. An optical element comprising the cured product according to claim 8.

10. The optical element according to claim 9 which is a lens.

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