Naphthalene compounds, methods for synthesizing the same, and compositions containing the naphthalene compounds

Abstract

The present invention provides a novel naphthalene compound, a method for synthesizing the naphthalene compound, and a composition containing the naphthalene compound. The naphthalene compound of the present invention has a high refractive index, and compositions containing the naphthalene compound can be applied to coatings, inks, adhesives, sealants, gas barrier films, color filters, optical films, optical lenses, and touch panels. [Solution] The present invention relates to a naphthalene compound represented by the following formula (I-4-9), and the method for synthesizing the naphthalene compound is to react a naphthalene dithiol compound with a dihaloalkane compound having 2 to 12 carbon atoms to haloalkylate two thiol groups, and then react it with a base. TIFF2026143633000033.tif37128 Furthermore, a composition containing the obtained naphthalene compound is provided.

Description

[Technical Field]

[0001] This invention relates to a novel naphthalene compound, a method for synthesizing the naphthalene compound, and a composition containing the naphthalene compound. [Background technology]

[0002] Conventionally, various materials have been used as resins for optical materials, such as for various optical films and optical lenses. Generally, polymers of polymerizable monomers, in which polymerization proceeds by radical species, are used, and materials with high refractive index, such as sulfur-containing compounds and fluorene compounds having polymerizable functional groups, are preferred for the purpose of improving light extraction efficiency (for example, Patent Documents 1 and 2). However, the resins for optical materials reported to date still have room for improvement in terms of the low thermal expansion, heat resistance, and mechanical strength of their cured products.

[0003] Furthermore, naphthalene compounds possessing both a naphthalene skeleton with a high refractive index and a sulfur element within the molecule have not been previously known to be used as resins for optical materials. In addition, analogues with two polymerizable functional groups introduced into the molecule have not been reported. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-94987 [Patent Document 2] Japanese Patent Publication No. 2010-248358 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a novel naphthalene compound, a method for synthesizing the naphthalene compound, and a composition containing the naphthalene compound. [Means for solving the problem]

[0006] The inventors of the present invention have conducted intensive studies to solve the above problems, and have found that the intended object can be achieved by a naphthalene compound obtained by reacting a certain naphthalenedithiol compound with a certain styrene compound, alkyne compound or alkene compound, and thus completed the present invention. That is, the first invention is a naphthalene compound represented by chemical formula (I).

[0007]

Chemical Formula

[0008]

Chemical Formula

[0009] The second invention is a method for synthesizing the naphthalene compound according to the first invention, which is characterized by reacting a naphthalenedithiol compound represented by chemical formula (II) with a styrene compound represented by chemical formula (III), an alkyne compound represented by chemical formula (IV) or an alkene compound represented by chemical formula (V).

[0010]

Chemical Formula

[0011]

Chemical Formula

[0012] The third invention is a naphthalene compound represented by chemical formula (I) among the naphthalene compounds of the first invention, and R 1 However, the method for synthesizing a compound that is identical and has a group represented by formula (3) is characterized by reacting a naphthalenedithiol compound represented by chemical formula (II) with a dihaloalkane compound having 2 to 12 carbon atoms to haloalkylate two thiol groups (first step), and then reacting the resulting compound with a base (second step).

[0013] The fourth invention is a composition characterized by containing the naphthalene compound of the first invention. [Effects of the Invention]

[0014] The naphthalene compound of the present invention is a novel compound characterized by its high refractive index. Because this naphthalene compound has two polymerizable groups within its molecule, it is useful as a material for optical applications. Furthermore, it is expected to exhibit higher compatibility with various solvents and resin components compared to conventional optical materials. The composition containing the naphthalene compound of the present invention is expected to yield a cured product with superior low thermal expansion, heat resistance, and mechanical strength compared to conventional compositions. Furthermore, it is expected to yield a cured product with a high refractive index. The compositions of the present invention can be applied to coating materials, inks, adhesives, sealants, gas barrier films, color filters, optical films, optical lenses, and touch panels, etc. [Brief explanation of the drawing]

[0015] [Figure 1] This is the IR spectrum chart of the white crystal obtained in Example 1. [Figure 2] This is the IR spectrum chart of the pale yellow crystal obtained in Example 2. [Figure 3] This is the IR spectral chart of the pale yellow solid obtained in Example 3. [Figure 4]This is the IR spectral chart of the white crystal obtained in Example 4. [Figure 5] This is the IR spectrum chart of the pale yellow crystal obtained in Example 5. [Figure 6] This is the IR spectrum chart of the pale yellow liquid obtained in Example 6. [Figure 7] This is the IR spectrum chart of the pale yellow crystal obtained in Example 7. [Figure 8] This is the IR spectrum chart of the pale yellow liquid obtained in Example 8. [Figure 9] This is the IR spectrum chart of the white crystal obtained in Example 9. [Modes for carrying out the invention]

[0016] The present invention will be described in detail below. 1. Naphthalene compounds The present invention relates to a naphthalene compound represented by the above chemical formula (I) (hereinafter sometimes referred to as "the naphthalene compound of the present invention"). The naphthalene compound represented by chemical formula (I) includes the naphthalene compounds represented by chemical formulas (I-1) to (I-5).

[0017] [ka] (In the formula, R 1 (This is the same as above.)

[0018] Examples of naphthalene compounds represented by chemical formula (I-1) include those represented by chemical formulas (I-1-1) to (I-1-9). Examples of naphthalene compounds represented by chemical formula (I-2) include those represented by chemical formulas (I-2-1) to (I-2-9). Examples of naphthalene compounds represented by chemical formula (I-3) include those represented by chemical formulas (I-3-1) to (I-3-12). Examples of naphthalene compounds represented by chemical formula (I-4) include those represented by chemical formulas (I-4-1) to (I-4-9). Examples of naphthalene compounds represented by chemical formula (I-5) include those represented by chemical formulas (I-5-1) to (I-5-9).

[0019] [ka]

[0020] [ka]

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] R 1 The group represented by formula (1) is the group shown in formulas (1-1) to (1-3).

[0025] [ka] (In the formula, Y 1 (This is the same as above.)

[0026] In the naphthalene compound of the present invention, R1 preferably represents (i) groups which are the same or different and are represented by formula (1-1) to formula (1-3), (ii) groups which are the same and are represented by formula (2), or (iii) groups which are the same and are represented by formula (3).

[0027] Y 1 Examples of the alkylene group having 1 to 10 carbon atoms represented by include linear or branched alkylene groups having 1 to 10 carbon atoms, and specific examples thereof include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. In the naphthalene compound of the present invention, Y 1 are preferably the same, and are preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms.

[0028] Examples of the method for synthesizing the naphthalene compound of the present invention include synthesis methods (1) and (2).

[0029] <Synthesis Method (1)> The naphthalene compound of the present invention can be synthesized by reacting a naphthalenedithiol compound represented by chemical formula (II) with a styrene compound represented by chemical formula (III), an alkyne compound represented by chemical formula (IV), or an alkene compound represented by chemical formula (V) (see reaction scheme (A) described later for a specific example).

[0030] The naphthalenedithiol compound represented by chemical formula (II) includes naphthalenedithiol compounds represented by chemical formula (II-1) to chemical formula (II-5). Furthermore, the naphthalenedithiol compound represented by chemical formula (II-1) is a precursor of the naphthalene compound represented by chemical formula (I-1), the naphthalenedithiol compound represented by chemical formula (II-2) is a precursor of the naphthalene compound represented by chemical formula (I-2), the naphthalenedithiol compound represented by chemical formula (II-3) is a precursor of the naphthalene compound represented by chemical formula (I-3), the naphthalenedithiol compound represented by chemical formula (II-4) is a precursor of the naphthalene compound represented by chemical formula (I-4), and the naphthalenedithiol compound represented by chemical formula (II-5) is a precursor of the naphthalene compound represented by chemical formula (I-5).

[0031] [ka]

[0032] These naphthalenedithiol compounds can be purchased and used as commercially available reagents.

[0033] In the styrene compound represented by chemical formula (III), the halogen atom represented by X may be, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and preferably a chlorine atom, a bromine atom, or an iodine atom. Examples of styrene compounds represented by chemical formula (III) include those represented by chemical formulas (III-1) to (III-7).

[0034] [ka]

[0035] These styrene compounds can be purchased and used as commercially available reagents.

[0036] Examples of alkyne compounds represented by chemical formula (IV) include those represented by chemical formulas (IV-1) to (IV-4).

[0037] [ka]

[0038] These alkyne compounds can be used by purchasing commercially available reagents, or they can be synthesized according to the method described in, for example, ACS Catalysis, 4(3), 722-731 (2014).

[0039] Examples of alkene compounds represented by chemical formula (V) include those represented by chemical formulas (V-1) to (V-3). [ka]

[0040] These alkene compounds can be used by purchasing commercially available reagents.

[0041] The amount of styrene compound represented by chemical formula (III), alkyne compound represented by chemical formula (IV), or alkene compound represented by chemical formula (V) used (charged) is preferably in an appropriate ratio within the range of 1.5 to 5.0 times the molar amount of naphthalenedithiol compound represented by chemical formula (II).

[0042] A specific example is shown in reaction scheme (A). The naphthalene compound of the present invention, represented by chemical formula (I-1-1), can be synthesized by reacting a naphthalenedithiol compound represented by chemical formula (II-1) with a styrene compound represented by chemical formula (III-1).

[0043] [ka]

[0044] In carrying out this reaction, it is preferable to use a base (a) to remove the acid produced as a by-product during the reaction. Additionally, a reaction solvent (b) may be used as needed.

[0045] Examples of bases (a) include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-(N,N-dimethylamino)pyridine, picoline, N,N-dimethylaniline, N,N-diethylaniline, imidazole, lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate Examples include potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxide (lithium methoxide, etc.), sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), potassium alkoxide (t-butoxypotassium, etc.), etc. These may be used individually or in combination of two or more.

[0046] The amount of base (a) used (charged) is preferably in an appropriate ratio within the range of 1.5 to 10.0 times the molar amount of the naphthalenedithiol compound represented by chemical formula (II).

[0047] The reaction solvent (b) is not particularly limited as long as it does not inhibit the reaction, and examples include solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethyl phosphate triamide, and water. These can be combined as needed and used in appropriate amounts.

[0048] In this reaction, the reaction temperature is preferably set within the range of 0 to 120°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set within the range of 1 to 24 hours.

[0049] After the reaction is complete, the naphthalene compound of the present invention, which is the target product of this invention, can be extracted from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization.

[0050] <Synthesis method (2)> The present invention relates to a naphthalene compound represented by chemical formula (I), wherein R 1 However, the compound that is identical and has the group shown in formula (3) can be synthesized by reacting a naphthalenedithiol compound shown in chemical formula (II) with a dihaloalkane compound having 2 to 12 carbon atoms to haloalkylate the two thiol groups (step 1), and then reacting the resulting compound with a base (step 2) (see reaction scheme (B) below for a specific example).

[0051] Examples of dihaloalkane compounds having 2 to 12 carbon atoms include compounds in which one hydrogen atom on each of the carbon atoms at both ends of a chain of alkanes having 2 to 12 carbon atoms is replaced by a halogen atom (such as a chlorine atom, bromine atom, or iodine atom). Examples include 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,3-dichloropropane, 1,3-dibromopropane, 1,3-diiodopropane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,4-diiodobutane, 1,5-dichloropentane, and 1,6-dichlorohexane.

[0052] In the first step of the reaction, the amount of dihalogen compound used (charge amount) is preferably in an appropriate ratio within the range of 2 to 100 molars relative to the amount of naphthalenedithiol compound used (charge amount) represented by chemical formula (II).

[0053] A specific example is shown in reaction scheme (B). The naphthalene compound of the present invention, represented by chemical formula (I-3-12), can be synthesized by reacting a naphthalenedithiol compound represented by chemical formula (II-3) with a dihalogen compound (step 1), and then reacting the resulting compound with a base (step 2).

[0054] [ka]

[0055] In carrying out the first step, it is preferable to use a base (a) to remove the acid produced as a by-product of the reaction. Additionally, a reaction solvent (b) may be used as needed. The base (a) and reaction solvent (b) can be those exemplified in synthesis method (1).

[0056] The amount of base (a) used (charged) is preferably in an appropriate proportion within the range of 2 to 10 times the molar amount of the naphthalenedithiol compound represented by chemical formula (II).

[0057] In the first step of the reaction, the reaction temperature is preferably set in the range of 30 to 120°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set in the range of 1 to 30 hours.

[0058] After the reaction in the first step is complete, the target naphthalene compound having halogen atoms can be extracted from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization. Furthermore, the naphthalene compound containing halogen atoms may be subjected to the aforementioned concentration, extraction, and purification processes before being used in the second step, or it may be used in the second step as is after the reaction in the first step is complete.

[0059] As the base used in the second step, base (a) exemplified in synthesis method (1) can be used. The amount of base used (amount added) is preferably in an appropriate ratio within the range of 2 to 20 times the molar amount of the naphthalene compound containing halogen atoms used (amount added).

[0060] In carrying out the second step, reaction solvent (b) may be used as appropriate, if necessary. The reaction solvent (b) can be the one exemplified in synthesis method (1).

[0061] In the second step of the reaction, the reaction temperature is preferably set within the range of -10 to 100°C. The reaction time is set appropriately according to the set reaction temperature, but it is preferably set within the range of 1 to 30 hours.

[0062] After the reaction in the second step is complete, the naphthalene compound of the present invention, which is the target product, can be extracted from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization.

[0063] 2. A composition containing a naphthalene compound (hereinafter sometimes referred to as "the composition of the present invention") The composition of the present invention contains the naphthalene compound of the present invention (hereinafter sometimes referred to as the "first curable compound") as an essential component, but may also contain one or more of the naphthalene compounds of the present invention. The content of the naphthalene compound of the present invention in the composition of the present invention is preferably 0.001 to 100% by weight, more preferably 0.001% by weight or more and less than 100% by weight, and particularly preferably 10% by weight or more and less than 90% by weight.

[0064] A cured product can be obtained by polymerizing the naphthalene compound of the present invention. In other words, since the composition of the present invention contains a naphthalene compound having carbon-carbon unsaturated bonds (double bonds, triple bonds) in its molecule, it can be described as a polymerizable or curable composition. By coexisting with another curable compound during polymerization, a cured product can be obtained in which the naphthalene compound of the present invention and the other curable compound are copolymerized. Other curable compounds include ene compounds having a carbon-carbon double bond in the molecule (hereinafter sometimes referred to as "second curable compound") and compounds having an epoxy group, oxetane ring, episulfide group, or vinyl group in the molecule (hereinafter sometimes referred to as "third curable compound").

[0065] (First composition) The first composition of the present invention contains the naphthalene compound of the present invention as an essential component, and optionally contains a second curable compound (an ene compound having a carbon-carbon double bond in the molecule). In this composition, the naphthalene compound of the present invention is R 1 However, it is preferable to use a naphthalene compound having (i) the same or different group represented by formula (1), or (ii) the same group represented by formula (2). For example, compounds represented by chemical formulas (I-1-1), (I-1-7), (I-1-9), (I-2-1), (I-2-7), (I-2-9), (I-3-1), (I-3-10), or (I-3-12) are preferred. Furthermore, from the viewpoint of compatibility with various solvents and resin components, R is used as the first curable compound. 1However, it is preferable to use a mixture of naphthalene compounds in which the group represented by formula (1) has different bonding positions of the vinyl group in formula (1) (for example, a mixture of the compound represented by chemical formula (I-3-1), the compound represented by chemical formula (I-3-2), the compound represented by chemical formula (I-3-4), and the compound represented by chemical formula (I-3-7). The second type of curable compound includes both polymerizable monomers and polymerizable oligomers (semi-cured products) having a structure in which polymerizable monomers are partially polymerized.

[0066] Examples of polymerizable monomers include, (1) Alkyl methacrylate monomers, (2) Hydroxyl group-containing monomers, (3) Carboxylate group-containing monomers, (4) Amino group-containing monomers, (5) Acetoacetyl group-containing monomers, (6) Isocyanate group-containing monomers, (7) Glycidyl group-containing monomers, (8) A monomer containing one or more aromatic rings, (9) Monomers containing an alkoxy group and an oxyalkylene group, (10) Alkoxyalkyl(meth)acrylamide monomers, (11) (meth)acrylamide monomers, (12) Monofunctional unsaturated compounds, (13) Examples include polyfunctional unsaturated compounds.

[0067] (1) Examples of alkyl ester monomers of (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, polyisobornyl (meth)acrylate, etc.

[0068] (2) Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate; and other monomers such as 2-acryloyloxyethyl 2-hydroxyethyl Examples include primary hydroxyl group-containing monomers such as taric acid, N-methylol(meth)acrylamide, and hydroxyethylacrylamide; secondary hydroxyl group-containing monomers such as 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-chloro2-hydroxypropyl(meth)acrylate, propylene glycol diglycidyl ether-epoxydi(meth)acrylate, phenol glycidyl ether-epoxy(meth)acrylate, and bisphenol A diglycidyl ether-epoxydi(meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl2-hydroxyethyl(meth)acrylate.

[0069] (3) Examples of carboxyl group-containing monomers include (meth)acrylic acid, acrylate dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid, etc.

[0070] (4) Examples of amino group-containing monomers include tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate.

[0071] (5) Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0072] (6) Examples of isocyanate group-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0073] (7) Examples of glycidyl group-containing monomers include epoxy(meth)acrylates which are reaction products of epoxy compounds such as glycidyl (meth)acrylate, ethylene glycol diglycidyl ether-epoxy(meth)acrylate, resorcinol diglycidyl ether-epoxy(meth)acrylate, bis(4-hydroxyphenyl) sulfide diglycidyl ether-epoxy(meth)acrylate, phenol novolac type epoxy resin-(meth)acrylate, cresol novolac type epoxy resin-(meth)acrylate, bisphenol (e.g., bisphenol A, bisphenol F) type epoxy resin-(meth)acrylate, biphenol (e.g., 3,3′,5,5′-tetramethylbiphenol) type epoxy resin-(meth)acrylate, and 1,3,5-tris(2,3-epoxypropyl) isocyanurate-(meth)acrylate with (meth)acrylic acid; and glycidyl(meth)acrylates such as 4-hydroxybutyl(meth)acrylate glycidyl ether.

[0074] (8) Examples of monomers containing one or more aromatic rings include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, naphthyl (meth)acrylate, biphenylmethyl (meth)acrylate, styrene, α-methylstyrene, vinylnaphthalene, etc.

[0075] (9) Examples of monomers containing alkoxy groups and oxyalkylene groups include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, and the like.

[0076] (10) Examples of alkoxyalkyl(meth)acrylamide monomers include methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, isopropoxymethyl(meth)acrylamide, n-butoxymethyl(meth)acrylamide, isobutoxymethyl(meth)acrylamide, and the like.

[0077] (11) Examples of (meth)acrylamide monomers include (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and (meth)acrylamide N-methylol(meth)acrylamide.

[0078] (12) Examples of monofunctional unsaturated compounds include biphenyl structure-containing (meth)acrylate compounds, more specifically biphenyl (meth)acrylates such as o-biphenyl (meth)acrylate, m-biphenyl (meth)acrylate, and p-biphenyl (meth)acrylate; biphenyloxyalkyl (meth)acrylates such as o-biphenyloxymethyl (meth)acrylate, m-biphenyloxymethyl (meth)acrylate, p-biphenyloxymethyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, m-biphenyloxyethyl (meth)acrylate, p-biphenyloxyethyl (meth)acrylate, o-biphenyloxypropyl (meth)acrylate, m-biphenyloxypropyl (meth)acrylate, and p-biphenyloxypropyl (meth)acrylate; (o-biphenyloxy)diethylene glycol (meth)acrylate, (m- Examples of biphenyloxy polyalkylene glycol (meth)acrylates include (b-biphenyloxy)diethylene glycol (meth)acrylate, (p-biphenyloxy)diethylene glycol (meth)acrylate, (o-biphenyloxy)dipropylene glycol (meth)acrylate, (m-biphenyloxy)dipropylene glycol (meth)acrylate, (p-biphenyloxy)dipropylene glycol (meth)acrylate, (o-biphenyloxy)polyethylene glycol (meth)acrylate, (m-biphenyloxy)polyethylene glycol (meth)acrylate, (p-biphenyloxy)polyethylene glycol (meth)acrylate, (o-biphenyloxy)polypropylene glycol (meth)acrylate, (m-biphenyloxy)polypropylene glycol (meth)acrylate, and (p-biphenyloxy)polypropylene glycol (meth)acrylate.

[0079] (13) Examples of polyfunctional unsaturated compounds include difunctional monomers, monomers with three or more functions, urethane (meth)acrylates, polyurethane (meth)acrylates, thiourethane (meth)acrylates, polythiourethane (meth)acrylates, the aforementioned epoxy (meth)acrylates, ester (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, (meth)acrylates having a cardo structure, sulfur-containing (meth)acrylates, vinyl thioethers, etc.

[0080] Specific examples of difunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A type di(meth)acrylate, and propylene oxide. Examples include modified bisphenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate diglycidyl ester di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, isocyanurate ethylene oxide modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0081] Furthermore, specific examples of monomers with three or more functionalities include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, and glycerin polyglyceride. Examples include zyl ether poly(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, isocyanurate ethylene oxide-modified tri(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, succinate-modified pentaerythritol tri(meth)acrylate, and the like.

[0082] A specific example of (meth)acrylates having a cardi structure is the compound shown in chemical formula (VI).

[0083] [ka] (In the formula, R 2 and R 3 (The 'a' represents a hydrogen atom or a methyl group, either identical or different. 'a' represents an integer from 1 to 4, either identical or different.)

[0084] A specific example of sulfur-containing (meth)acrylates is the compound shown by chemical formula (VII).

[0085] [ka] (In the formula, R 4R represents an alkyl group having 1 to 5 carbon atoms, which may be the same or different. 5 (b represents a hydrogen atom or a methyl group, either identical or different. b represents 0 or 1, either identical or different.)

[0086] In addition to the polymerizable monomers mentioned above, other examples include divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ethers, vinyltoluene, vinylpyridine, vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinyl Examples include ketones, 2-chloroethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluryl, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid trialyl ester, trifluoroethyl (meth)acrylate, tribromobenzyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, sulfur-containing polyfunctional (meth)acrylate, (meth)acryloyloxypropyltris(methoxy)silane, and thiophene compounds having a styryl group (e.g., (3-vinylbenzyl)-2-thiophene carboxylate, (4-vinylbenzyl)-2-thiophene carboxylate, etc.).

[0087] The first composition of the present invention contains the naphthalene compound of the present invention as an essential component, and optionally contains the second curable compound described above. The second curable compound may be a combination of the polymerizable monomer and polymerizable oligomer described above, and the polymerizable monomer may be a combination of the polymerizable monomers exemplified above (a combination of different types of polymerizable monomers may be used), and the polymerizable oligomer may also be a combination of different types of polymerizable oligomers. Regarding the ratio of the content of the naphthalene compound of the present invention and the second curable compound in the first composition of the present invention, it is preferable that the content of the second curable compound be in an appropriate ratio within the range of 0 to 1000 times (weight ratio) relative to the content of the naphthalene compound of the present invention, and more preferably in an appropriate ratio within the range of 0.01 to 100 times (weight ratio).

[0088] In the first composition of the present invention, a thiol compound may be contained as a curing agent. Examples of thiol compounds include aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, torylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); and chemical formula ( Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds as shown in VIII); mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; mercaptopropionic acid esters such as trimethylolpropanetris(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptopropionate); epoxy resin-terminated mercapto compounds; 3,6-dioxa-1,8-octanedithiol and pentaerythritol Tripropanethol, 1,2,3-(3-mercaptopropyloxy)propane, mercaptoalkyl ether disulfide compound represented by chemical formula (IX), 2,2′-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3′-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethol, 3-[2,2-bis[(3-mercaptopropyl Examples include mercaptoalkyl ether compounds such as ropoxy)methyl]butoxy]-1-propanthol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, and 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; and 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluryl and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluryl, which may be used in combination.

[0089] [ka] (In the formula, p represents an integer between 1 and 5.)

[0090] [ka] (In the formula, q represents an integer between 1 and 20.)

[0091] In the first composition of the present invention, the content of the thiol compound is preferably 0.1 to 100 parts by weight, and more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0092] The first composition of the present invention may contain a reactive diluent. In this specification, a reactive diluent means a compound having one epoxy group (glycidyl group) and having a relatively low viscosity at room temperature. Depending on the purpose, the reactive diluent may have other polymerizable functional groups besides epoxy groups, such as alkenyl groups like vinyl and allyl; or unsaturated carboxylic acid residues like acryloyl and methacryloyl.

[0093] Examples of reactive diluents include monoepoxide compounds such as n-butylglycidyl ether, 2-ethylhexylglycidyl ether, phenylglycidyl ether, cresylglycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allylglycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0094] In the first composition of the present invention, the content of the reactive diluent is preferably 1 to 400 parts by weight per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0095] Methods for polymerizing (curing) the first composition of the present invention include photocuring and thermal curing. Methods for photocuring include irradiation with active energy rays, preferably in combination with a photopolymerization initiator. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As light sources, for example, a high-pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. In addition, light sources such as lasers and LEDs that emit light at various wavelengths, which have become increasingly popular in recent years, may also be used. The amount of active energy ray irradiation can be appropriately set according to the type of light source, etc.

[0096] The photopolymerization initiator can be selected from photoradical polymerization initiators, photoanionic polymerization initiators, and photocationic polymerization initiators, and any of these can be included in the composition. In addition, thermal polymerization (thermosetting) may be used in combination with photocuring to improve production efficiency and the properties of the cured product.

[0097] As a photoradical polymerization initiator, any commonly used photoradical polymerization initiator can be used without particular restrictions, but examples include acetophenones such as acetophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, acetophenone dimethyl ketal, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, etc.; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzo Benzoins such as isopropyl ether and benzoin isobutyl ether; benzophenone, hydroxybenzophenone, o-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 4,4′-bis(methylamino)benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-hydroxybenzoic acid] Benzophenones such as so-2-propenyloxy)ethyl]benzenemethanaminonium bromide and (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride;Examples include acyl phosphonate oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and methylphenylglyoxylate. These may be used individually or in combination of two or more.

[0098] As a photoanionic polymerization initiator, any commonly used one can be used without particular restrictions, such as onium salts and carbamates. Examples of onium salts include 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, while examples of carbamates include 2-nitrophenylmethylpiperidine-1-carboxylate, 1-(anthraquinone-2-yl)ethylimidazole carboxylate, 1-(3-(2-hydroxyphenyl)-2-propenoyl)piperidine and 9-anthranylmethyldiethylcarbamate.

[0099] As photocationic polymerization initiators, any commonly used ones can be used without particular restrictions, including onium salts and organometallic complexes. Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts, while examples of organometallic complexes include iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of commercially available photocationic polymerization initiators include "ADEKA Optomer SP-150" and "ADEKA Optomer SP-170" from ADEKA Corporation, "UVE-1014" from General Electronics Corporation, "CD-1012" from Sartomer Corporation, and "CPI-100P" from Sunapro Corporation. SbF6 is used as the counteranion for photocationic polymerization initiators. - AsF6 - , B(C6F5)4 - PF6 - These are some examples.

[0100] In the first composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0101] Furthermore, the first composition of the present invention may contain an auxiliary agent for photoradical polymerization initiators. Examples of auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0102] In addition, the first composition of the present invention may contain a sensitizer to expand the photosensitive wavelength range and increase sensitivity. Examples of sensitizers include benzophenone, p,p'-tetramethyldiaminobenzophenone, p,p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, thioxanthone, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, Examples include benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis(5,7-dimethoxycarbonylcoumarin), coronene, and others.

[0103] In the first composition of the present invention, the content of the sensitizer is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0104] On the other hand, a method for thermally curing the first composition of the present invention is to use a thermal polymerization initiator in combination. The thermal polymerization initiator can be selected from thermal radical polymerization initiators, thermal anionic polymerization initiators, and thermal cationic polymerization initiators, and any of them may be included in the composition. Regarding the conditions for thermosetting, the heating temperature and heating time can be set as appropriate, but it is preferable to set them in the range of 60 to 130°C / 30 to 240 minutes, and more preferably in the range of 70 to 125°C / 30 to 120 minutes. Heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a closed-type curing furnace or a tunnel furnace capable of continuous curing can be used as the curing apparatus.

[0105] As a thermal radical polymerization initiator, any commonly used one can be used without particular limitations, for example, diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate Examples of peroxides include t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1,1-bis(t-hexyl peroxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, and azo compounds such as azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), and dimethyl-2,2′-azobis(2-methylpropionate), and these may be used in combination.

[0106] As a thermal anionic polymerization initiator, any commonly used one can be used without particular restrictions, such as amines and imidazoles, and these may be used in combination. Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, and 1,3,4,6-tetrakis(3-aminopropyl)glycoluryl, while examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

[0107] As a thermal cationic polymerization initiator, any commonly used one can be used without particular limitations. Examples include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes, and these may be used in combination. Examples of commercially available onium salts include "ADEKA Opton CP-66" and "ADEKA Opton CP-77" from ADEKA Corporation, "San-Aid SI-60L," "San-Aid SI-80L," and "San-Aid SI-100L" from Sanshin Chemical Industry Co., Ltd., and the "CI Series" from Nippon Soda Co., Ltd. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0108] The content of the thermal polymerization initiator in the first composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight, based on the total amount of the composition.

[0109] The first composition of the present invention may further contain, insofar as it does not impede the effects of the present invention, pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.); inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopon, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, silica powder such as spherical silica, spherical alumina, broken Oxides such as crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, and zirconium oxide; nitrides such as boron nitride, silicon nitride, and aluminum nitride; carbides such as silicon carbide; hydroxides such as aluminum hydroxide and magnesium hydroxide; metals and alloys such as copper, silver, iron, aluminum, nickel, titanium, platinum, and gold; carbon-based materials such as diamond and carbon; thermoplastic resins and thermosetting resins (various high-density, medium-density, and low-density polyethylenes, polypropylene, polybutene, polypentene, and other homopolymers); Polyamide resins such as ethylene-propylene copolymer, nylon-6, nylon-6,6, etc., vinyl chloride resin, nitrocellulose resin, vinylidene chloride resin, acrylic resin (including curable compounds excluding the polymerizable monomers mentioned above), acrylamide resin, styrene resin, vinyl ester resin, polyester resin, phenolic resin (phenolic compound), epoxy resin (epoxy compound), silicone resin, fluororesin, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene graft copolymer, etc.); reinforcing agents (glass fiber, carbon fiber, etc.); anti-sagging agents (hydrogenated castor oil, fine particle anhydrous silicic acid, etc.); matting agents (fine silica powder, paraffin wax, etc.); abrasives (zinc stearate, etc.); internal release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearamide, fatty acid esters, polyolefin wax, paraffin wax, etc.);Diluents (organic solvents such as n-butyl alcohol, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), toluene, water, and mixtures of organic solvents and water); coupling agents (silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane); chain transfer agents (thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate)); and additives (modifiers) such as surfactants, leveling agents, defoamers, fragrances, flame retardants, and dyes may also be present.

[0110] The aforementioned thermoplastic and thermosetting resins include resins (compounds) having a cardi structure (a skeletal structure in which four aromatic rings are bonded to a carbon atom), as represented by chemical formula (X).

[0111] [ka] (In the formula, n represents the degree of polymerization.)

[0112] Examples of monomers having a cardo structure include 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis(cyanomethyl)fluorene, and 9,9-bis(3-aminopropyl)fluorene.

[0113] In the first composition of the present invention, the content of the additive (modifier) ​​may be in a proportion of 0.01 to 85% by weight relative to the total amount of the composition.

[0114] Table 1 shows preferred formulations (excluding organic solvents) in the first composition of the present invention.

[0115] [Table 1]

[0116] There are no particular limitations on the method for preparing the first composition of the present invention. For example, it can be prepared by mixing the naphthalene compound of the present invention with a second curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier); or by mixing a solution obtained by dissolving or dispersing the naphthalene compound of the present invention in a diluent (organic solvent) and / or a reactive diluent with a second curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier). Known methods can be used as means of mixing.

[0117] (Second composition) The second composition of the present invention contains the naphthalene compound of the present invention as an essential component, and optionally contains a third curable compound (a compound having an epoxy group, an oxetane ring, an episulfide group, or a vinyl group in its molecule). In this composition, the naphthalene compound of the present invention is R 1 However, (iii) it is preferable to use a naphthalene compound that is identical and has the group represented by formula (3) above. The third type of curable compound includes both polymerizable monomers and polymerizable oligomers (semi-cured products) having a structure in which polymerizable monomers are partially polymerized.

[0118] Examples of polymerizable monomers include known epoxy compounds (sometimes referred to as epoxy resins), oxetane compounds, epoxy-oxetane compounds (containing an oxirane ring and an oxetane ring in the molecule), episulfide compounds, vinyl monomers, and the like.

[0119] As for epoxy compounds, any compound having an oxirane ring (epoxy group / glycidyl group) in its molecule can be used without particular limitations. Examples include: polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidyl glycoluryl compounds having two or more epoxy groups in their molecule, such as 1,3,4,6-tetraglycidyl glycoluryl; 3 Examples include alicyclic epoxy compounds such as ',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and bicyclononadiene diepoxide; nitrogen-containing cyclic epoxy compounds such as triglycidyl isocyanurate and hydantoin-type epoxy compounds; and further, epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, as well as epoxy-modified organopolysiloxane compounds obtained by hydrosilylation addition reactions between organic compounds having a carbon-carbon double bond and a glycidyl group and silicon compounds having a SiH group (for example, epoxy-modified organopolysiloxane compounds disclosed in Japanese Patent Publication No. 2004-99751 and Japanese Patent Publication No. 2006-282988). These may be used in combination.

[0120] As for oxetane compounds, any compound having an oxetane ring (oxetanyl group / oxetane group) in its molecule can be used without particular restriction, for example, 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy) [methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether Tel, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, Butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3′-(1,3-(2-methyleneyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-Bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediylmethylene(3-ethyl-3-oxetanylmethyl) ether, trimethyl Tyrolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hex Sakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Examples include (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0121] The epoxy-oxetane compounds can be used without particular limitation as long as they have an oxirane ring (as above) and an oxetane ring (as above) in their molecule. Examples include those described in U.S. Patent No. 3,457,193, Japanese Patent Publication No. 2005-002191, Japanese Patent Publication No. 2007-270070, Japanese Patent Publication No. 2010-111713, or Japanese Patent Publication No. 2011-208089. These epoxy-oxetane compounds are included in the disclosure herein by reference to the epoxy-oxetane compounds described in these documents.

[0122] The episulfide compound can be used without any particular limitations as long as it has an episulfide group in its molecule. Examples include episulfide compounds obtained by episulfidizing some or all of the epoxy groups of the above-mentioned epoxy compound. Other examples include thiran methanethiol, 2,2'-bis[9H-fluorene-9-ylidenebis(6,2-phenyleneoxymethylene)] thiran, 2,2'-bis[9H-fluorene-9-ylidenebis(6,2-naphthyleneoxymethylene)] thiran, and episulfide compounds having unsaturated groups such as vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, and allylthioglycidyl ether.

[0123] Any vinyl monomer that can be cationically polymerized can be used without particular limitations. Examples include styrenes, alkenyl ethers, indene, and N-vinylcarbazole, with styrenes and alkenyl ethers being preferred. Examples of styrenes include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene. Alkenyl ethers include, for example, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, n-amyl vinyl ether, and isoamyl vinyl ether; fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, and 2,2,2-trifluoroethyl vinyl ether; alkoxyalkyl vinyl ethers such as 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-tetrahydropyranyl vinyl ether, and 2-tetrahydrofuranyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether, cyclooctyl vinyl ether, 2-bicyclo[2.2.1]heptyl vinyl ether, 2-bicyclo[2.2.2]octyl vinyl ether, and 8-tricyclo[5.2.1.0 2,6 Examples include cycloalkyl vinyl ethers such as decanyl vinyl ether, 1-adamantyl vinyl ether, and 2-adamantyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether, 4-methylphenyl vinyl ether, 4-trifluoromethylphenyl vinyl ether, and 4-fluorophenyl vinyl ether; and arylalkyl vinyl ethers such as benzyl vinyl ether and 4-fluorobenzyl vinyl ether.

[0124] The second composition of the present invention contains the naphthalene compound of the present invention as an essential component, and optionally contains the third curable compound described above. This third curable compound may be a combination of the polymerizable monomer and polymerizable oligomer described above, and the polymerizable monomer may be a combination of the polymerizable monomers exemplified above (a combination of different types of polymerizable monomers may be used), and the polymerizable oligomer may also be a combination of different types of polymerizable oligomers. Regarding the respective content ratios of the naphthalene compound of the present invention and the third curable compound in the second composition of the present invention, it is preferable that the content of the third curable compound be in an appropriate proportion within the range of 0 to 1000 times (weight ratio) relative to the content of the naphthalene compound of the present invention, and more preferably in an appropriate proportion within the range of 0.01 to 100 times (weight ratio).

[0125] Methods for polymerizing (curing) the second composition of the present invention include photocuring and thermal curing. Methods for photocuring include irradiation with active energy rays, preferably in combination with a photopolymerization initiator. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As light sources, for example, a high-pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. In addition, light sources such as lasers and LEDs that emit light at various wavelengths, which have become increasingly popular in recent years, may also be used. The amount of active energy radiation irradiated can be set appropriately depending on the type of light source and other factors.

[0126] As the photopolymerization initiator, a photocationic polymerization initiator can be used, and if necessary, a photoradical polymerization initiator can be used in combination, and these can be included in the composition. In addition, in photocuring, thermal curing methods may be used in combination to improve production efficiency and the properties of the cured product.

[0127] As a photocationic polymerization initiator, any commonly used one can be used without particular limitations, such as onium salts and organometallic complexes. As a photocationic polymerization initiator, the photocationic polymerization initiator described in the section on the first composition can be used. The content of the photocationic polymerization initiator in the second composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0128] As the photoradical polymerization initiator, the photoradical polymerization initiator described in the section on the first composition can be used. The content of the photoradical polymerization initiator in the second composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0129] Furthermore, when photocuring the second composition of the present invention, the sensitizer described in the section on the first composition can be used.

[0130] On the other hand, when thermally curing the second composition of the present invention, a thermal polymerization initiator can be used. A thermal cationic polymerization initiator can be used as the thermal polymerization initiator, and this can be included in the composition. Heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a closed-type curing furnace or a tunnel furnace capable of continuous curing can be used as the curing apparatus. The heating (curing) temperature and heating (curing) time should be set appropriately, taking into consideration the composition and shape (thickness) of the object to be irradiated.

[0131] As a thermal cationic polymerization initiator, any commonly used one can be used without particular limitations, including various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, and organometallic complexes. As a thermal cationic polymerization initiator, the thermal cationic polymerization initiator described in the section on the first composition can be used. The content of the thermal cationic polymerization initiator in the second composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0132] The second composition of the present invention may further contain, if necessary, the additive (modifier) ​​described in the section on the first composition, in a proportion of 0.01 to 85% by weight relative to the entire second composition (total amount), provided that it does not inhibit the effects of the present invention.

[0133] Table 2 shows preferred formulations (excluding organic solvents) in the second composition of the present invention.

[0134] [Table 2]

[0135] There are no particular limitations on the method for preparing the second composition of the present invention; it can be prepared by measuring out predetermined amounts of each of the aforementioned components and stirring and mixing them. For example, after pre-mixing, it can be prepared by mixing or melt-kneading using a roll kneader, kneader, extruder, etc. If necessary, an organic solvent (viscosity adjusting diluent) may be used.

[0136] 3.Applications The compositions of the present invention (hereinafter, including "the first composition" and "the second composition") are expected to provide cured products with low thermal expansion, heat resistance, and excellent mechanical strength. Furthermore, they are expected to provide cured products with a high refractive index. Therefore, the compositions of the present invention are suitable as materials used in the manufacture of coating materials, inks, adhesives, sealants, gas barrier films, color filters, optical films, optical lenses, and touch panels.

[0137] Applications of the aforementioned coating material include protection (hard coating) of touch panels, plastic containers, plastic sheets, plastic films, film-type liquid crystal elements, polarizing plates used in liquid crystal display devices, optical components, and building interior materials (flooring, wall materials, artificial marble, etc.).

[0138] Examples of the aforementioned inks include colored inks, printing inks, UV inks, and inkjet inks. These inks are used in offset printing, flexographic printing, gravure printing, screen printing, inkjet printing, and the like.

[0139] Applications of the aforementioned adhesive include semiconductors, optics, optical components, optical waveguide coupling, fixing peripheral components of optical waveguides, and CD / DVD bonding.

[0140] Applications of the aforementioned adhesive include adhesive tapes, adhesive sheets, adhesive labels, and the like.

[0141] Applications of the aforementioned gas barrier film include electronic paper, flexible displays, organic EL elements, and organic solar cells.

[0142] Applications of the aforementioned color filters include color liquid crystal display devices (color filter on array (COA)), color image sensors, and organic EL display devices.

[0143] Examples of the aforementioned optical films include protective films for polarizing plates, films for liquid crystal display devices such as support films for prism sheets and light guide films, hard coat films, functional films such as decorative films and transparent conductive films, weather-resistant (light-resistant) films for solar cells, films for LED lighting and organic EL lighting, and transparent heat-resistant films for flexible electronics.

[0144] Examples of the aforementioned optical lenses include lenses for microscopes, endoscopes, telescopes, cameras, eyeglasses, optical cover lenses, refractive index distribution lenses, Fresnel lenses, lenses for smart glasses, lenticular lenses, VR lenses, AR lenses, lenses for laser beam printers, sensor lenses, prism lenses, and pickup lenses for optical discs.

[0145] Applications of the aforementioned touch panels include personal computers, car navigation systems, mobile phones, electronic dictionaries, and office automation / factory automation equipment.

[0146] The compositions of the present invention can further be used in various optical materials such as transparent materials, high refractive index layers of anti-reflective coatings, optical thin films such as reflectors, core materials and cladding materials for optical fibers, optical waveguides, holograms, dicing tapes, insulating materials (wire coatings, etc.), solder resist inks, printed circuit boards, copper-clad laminates, resin-coated copper foil, prepregs, high-voltage insulating materials, interlayer insulating materials, passivation films for TFTs, gate insulating films for TFTs, interlayer insulating films for TFTs, transparent planarization films for TFTs, insulating packings, insulating coatings, paints, UV powder coatings, molding materials (sheets, films, FRP, etc.), sealing materials, liquid crystal sealing materials, sealing materials for display devices, high heat-resistant sealing materials, potting materials, encapsulating materials (semiconductor encapsulating materials, encapsulating materials for electrical materials, encapsulating materials for organic EL and LED elements, encapsulating materials for various solar cells), and resist materials (liquid resists). In addition to materials used in the electrical and electronic fields such as materials, colored resist materials, dry film resist materials, solder resist materials, color filter resist materials, photospacer materials for liquid crystal cells, photopolymerization, materials for solar cells, materials for fuel cells, display materials, recording materials, photosensitive drums for copiers, liquid crystal displays, microdisplays, light guide plates for liquid crystals, microlens arrays, Fresnel ROM waveplates, polarizing beam splitters, and solid electrolytes for batteries, it is also expected to be used as a raw material or component for vibration-damping materials, waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, gas separation membranes, concrete protective materials, linings, soil injection agents, thermal storage materials, sealing materials for sterilization equipment, and oxygen permeable membranes, as well as as an additive (modifier) ​​blended into other resins or resin compositions (thermoplastic, thermosetting, photocurable). [Examples]

[0147] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. The main raw materials used in the examples and comparative examples are as follows:

[0148] [Main raw materials] • 1,5-Naphthalenedithiol (manufactured by Sugai Chemical Industry Co., Ltd., see chemical formula (II-1)). • 2,6-Naphthalenedithiol (manufactured by Sugai Chemical Industry Co., Ltd., see chemical formula (II-2)). • 1,6-Naphthalenedithiol (manufactured by Sugai Chemical Industry Co., Ltd., see chemical formula (II-3)). • 4-Vinylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., see chemical formula (III-1)). • A mixture of 3-vinylbenzyl chloride and 4-vinylbenzyl chloride (manufactured by AGC Seimi Chemical, trade name "CSM-P", a mixture of chemical formulas (III-1) and (III-4)). • Propargyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd., see chemical formula (IV-2)). • 1,2-Dichloroethane (manufactured by Tokyo Chemical Industry Co., Ltd.) • Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) • t-Butoxypotassium (manufactured by Tokyo Chemical Industry Co., Ltd.) • Dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.) • Dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) • Toluene (manufactured by Wako Pure Chemical Industries) • Dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) • Hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.)

[0149] The evaluation test (measurement of refractive index) method used in the examples and comparative examples is as follows:

[0150] [Measuring the refractive index] For the compounds in the examples and comparative examples, measurement samples were prepared by dissolving them in dimethylformamide (DMF) to a concentration of 40% by weight (DMF solution). For the prepared DMF solution and DMF alone, the refractive index (at 25°C) was measured using an Abbe refractometer (NAR-1T SOLID, manufactured by Atago) in accordance with JIS K 0062 ("Method for Measuring the Refractive Index of Chemical Products"), under LED light (D-line wavelength). From the obtained measurements, the refractive indices of the compounds in the examples and comparative examples were calculated using the following formula. Refractive index = (Refractive index of DMF solution (compound concentration 40 wt%) - Refractive index of DMF alone) / 0.4 + Refractive index of DMF alone

[0151] [Example 1] <Synthesis of 1,5-bis{[(4-ethenylphenyl)methyl]thio}naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,5-naphthalenedithiol, 1.83 g (12.0 mmol) of 4-vinylbenzyl chloride, and 30 mL of 1,2-dichloroethane were charged, and 2.43 g (24.0 mmol) of triethylamine was added while stirring. Subsequently, the mixture was stirred at 50°C for 12 hours. The solution was then cooled to room temperature and insoluble matter was filtered off. The resulting filtrate was washed three times with 50 mL of water and concentrated under reduced pressure. The resulting concentrate was recrystallized with 10 mL of toluene to obtain 320 mg of white crystals (yield: 15%).

[0152] The obtained white crystal 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 8.37 (d, 2H), 7.08-7.54 (m, 12H),6.61-6.71 (m, 2H), 5.68 (dd, 2H), 5.23 (dd, 2H), 4.13 (s, 4H). Furthermore, the IR spectral data of this white crystal was as shown in the chart in Figure 1. Based on these spectral data, the obtained white crystals were identified as the naphthalene compound shown in the title, represented by chemical formula (I-1-1).

[0153] [Example 2] <Synthesis of 1,5-bis(2-propyne-1-ylthio)naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,5-naphthalenedithiol, 1.19 g (10.0 mmol) of propargyl bromide, and 30 mL of dichloromethane were charged, and 2.43 g (24.0 mmol) of triethylamine was added while stirring. The mixture was then stirred at room temperature for 12 hours. Subsequently, the insoluble matter was filtered off at room temperature. The obtained filtrate was washed three times with 50 mL of water and concentrated under reduced pressure. The resulting concentrate was recrystallized with 20 mL of toluene to obtain 850 mg of pale yellow crystals (yield: 63%).

[0154] The pale yellow crystals obtained 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 8.42 (d, 2H), 7.79 (d, 2H), 7.52 (dd, 2H), 3.65 (d, 4H), 2.20 (t, 2H). Furthermore, the IR spectral data of this pale yellow crystal was as shown in the chart in Figure 2. Based on these spectral data, the obtained pale yellow crystals were identified as the naphthalene compound shown in the title, represented by chemical formula (I-1-7).

[0155] [Example 3] <Synthesis of 1,5-bis(ethenylthio)-naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,5-naphthalenedithiol, 19.79 g (200.0 mmol) of 1,2-dichloroethane, and 30 mL of dimethylformamide were charged, and 1.42 g (14.0 mmol) of triethylamine was added while stirring. Subsequently, the temperature was raised to 60°C and the mixture was stirred at that temperature for 2 hours. The mixture was then cooled to room temperature, 30 mL of toluene was added, and the mixture was washed five times with 50 mL of water. Concentration under reduced pressure yielded 1.21 g of a pale yellow solid. Next, 1.21 g of the obtained pale yellow solid and 19.1 mL of dimethylacetamide were placed in a 100 mL flask, and the mixture was cooled to -10°C while stirring. 1.20 g (10.7 mmol) of t-butoxy potassium was added in portions, ensuring the temperature did not exceed 0°C. The mixture was then stirred at 0°C for 2 hours. Subsequently, 20 mL of toluene was added, and the mixture was washed five times with 30 mL of water. By performing vacuum concentration, 892 mg of a pale yellow solid was obtained (yield: 73%).

[0156] The pale yellow solid obtained 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 8.24 (d, 2H), 7.76 (d, 2H), 7.63-7.68 (m, 2H), 6.73 (dd, 2H), 5.43 (d, 2H), 5.16 (d, 2H). Furthermore, the IR spectral data for this pale yellow solid was as shown in the chart in Figure 3. Based on these spectral data, the obtained pale yellow solid was identified as the naphthalene compound shown in the title, represented by chemical formula (I-1-9).

[0157] [Example 4] <Synthesis of 2,6-bis{[(4-ethenylphenyl)methyl]thio}naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 2,6-naphthalenedithiol, 1.83 g (12.0 mmol) of 4-vinylbenzyl chloride, and 30 mL of dimethylacetamide were charged, and 1.42 g (14.0 mmol) of triethylamine was added while stirring. Subsequently, the mixture was stirred at 50°C for 8 hours. The solution was then cooled to room temperature and the insoluble matter was filtered off. The resulting filtrate was washed once with 40 mL of water after adding 80 mL of toluene, and then concentrated under reduced pressure. The resulting concentrate was poured into 150 mL of methanol to obtain 1.31 g of white crystals (yield: 62%).

[0158] The obtained white crystal 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 7.81 (d, 2H), 7.73 (d, 2H), 7.23-7.51 (m, 10H), 6.64-6.72 (m, 2H), 5.77 (dd, 2H), 5.22 (dd, 2H), 4.33(s, 4H). Furthermore, the IR spectral data of this white crystal was as shown in the chart in Figure 4. Based on these spectral data, the obtained white crystals were identified as the naphthalene compound shown in the title, represented by chemical formula (I-2-1).

[0159] [Example 5] <Synthesis of 2,6-bis(2-propyne-1-ylthio)naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 2,6-naphthalenedithiol, 1.19 g (10.0 mmol) of propargyl bromide, and 30 mL of dichloromethane were charged, and 2.43 g (24.0 mmol) of triethylamine was added while stirring. The mixture was then stirred at room temperature for 12 hours. Subsequently, the insoluble matter was filtered off at room temperature. The obtained filtrate was washed three times with 50 mL of water and concentrated under reduced pressure. The resulting concentrate was recrystallized with 20 mL of toluene to obtain 790 mg of pale yellow crystals (yield: 59%).

[0160] The pale yellow crystals obtained 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 8.87 (d, 2H), 7.75 (d, 2H), 7.52 (dd, 2H), 3.72 (d, 4H), 2.54 (t, 2H). Furthermore, the IR spectral data of this pale yellow crystal was as shown in the chart in Figure 5. Based on these spectral data, the obtained pale yellow crystals were identified as the naphthalene compound shown in the title, represented by chemical formula (I-2-7).

[0161] [Example 6] <Synthesis of 1,6-bis{[(4-ethenylphenyl)methyl]thio}naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,6-naphthalenedithiol, 1.56 g (10.2 mmol) of 4-vinylbenzyl chloride, and 30 mL of dichloromethane were charged, and 2.02 g (20.0 mmol) of triethylamine was added while stirring. The mixture was then stirred at room temperature for 12 hours. Subsequently, the insoluble matter was filtered off at room temperature. The obtained filtrate was washed three times with 50 mL of water and concentrated under reduced pressure. The resulting concentrate was washed with 30 mL of 2-propanol to obtain 590 mg of a pale yellow liquid (yield: 28%).

[0162] The pale yellow liquid obtained 1 The H-NMR spectral data were as follows: · 1 H-NMR (CDCl3) δ: 8.28 (d, 1H), 7.05-7.73 (m, 13H),6.58-6.72 (m, 2H), 5.70 (dd, 2H), 5.21 (dd, 2H), 4.20 (d, 2H), 4.09 (s, 2H). Furthermore, the IR spectral data of this pale yellow liquid was as shown in the chart in Figure 6. Based on these spectral data, the obtained pale yellow liquid was identified as the naphthalene compound shown in the title, represented by chemical formula (I-3-1).

[0163] [Example 7] <Synthesis of 1,6-bis(2-propyne-1-ylthio)naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,6-naphthalenedithiol, 1.19 g (10.0 mmol) of propargyl bromide, and 30 mL of dichloromethane were charged, and 2.43 g (24.0 mmol) of triethylamine was added while stirring. The mixture was then stirred at room temperature for 12 hours. Subsequently, the insoluble matter was filtered off at room temperature. The obtained filtrate was washed three times with 50 mL of water and concentrated under reduced pressure. The resulting concentrate was recrystallized with 20 mL of toluene to obtain 1.23 g of pale yellow crystals (yield: 91%).

[0164] The pale yellow crystals obtained 1 The H-NMR spectral data were as follows: · 1H-NMR (CDCl3) δ: 8.36 (d, 1H), 7.88 (d, 1H), 7.69-7.75 (m, 2H), 7.57 (dd, 1H), 7.44 (dd, 1H), 3.71 (d, 2H), 3.65 (d, 2H), 2.24 (t, 1H), 2.20 (t, 1H). Furthermore, the IR spectral data of this pale yellow crystal was as shown in the chart in Figure 7. Based on these spectral data, the obtained pale yellow crystals were identified as the naphthalene compound shown in the title, represented by chemical formula (I-3-10).

[0165] [Example 8] <Synthesis of 1,6-bis(ethenylthio)-naphthalene> In a 100 mL flask, 961 mg (5.0 mmol) of 1,6-naphthalenedithiol, 19.79 g (200.0 mmol) of 1,2-dichloroethane, and 30 mL of dimethylformamide were charged, and 1.42 g (14.0 mmol) of triethylamine was added while stirring. Subsequently, the temperature was raised to 60°C and stirred at the same temperature for 2 hours. The solution was then cooled to room temperature, 30 mL of toluene was added, and the mixture was washed five times with 50 mL of water. Concentration under reduced pressure yielded 1.32 g of a pale yellow liquid. Next, 1.32 g of the obtained pale yellow liquid and 20.8 mL of dimethylacetamide were placed in a 100 mL flask, and the mixture was cooled to -10°C while stirring. 1.31 g (11.7 mmol) of t-butoxy potassium was added in installments, ensuring the temperature did not exceed 0°C. The mixture was then stirred at 0°C for 2 hours. Subsequently, 21.8 mL of toluene was added, and the mixture was washed five times with 32.7 mL of water. By performing reduced-pressure concentration, 982 mg of a pale yellow liquid was obtained (yield: 80%).

[0166] The pale yellow liquid obtained 1 The H-NMR spectral data were as follows: · 1H-NMR (CDCl3) δ: 8.17 (d, 1H), 8.05 (d, 1H), 7.95 (d, 1H), 7.67 (d, 1H), 7.54-7.60 (m, 2H), 6.87 (dd, 1H), 6.71 (dd, 1H), 5.38-5.56 (m, 3H), 5.11 (d, 1H). Furthermore, the IR spectral data of this pale yellow liquid was as shown in the chart in Figure 8. Based on these spectral data, the obtained pale yellow liquid was identified as the naphthalene compound shown in the title, represented by chemical formula (I-3-12).

[0167] [Example 9] <Synthesis of mixtures of compounds represented by chemical formulas (I-3-1), (I-3-2), (I-3-4), and (I-3-7)> In a 1000 mL flask, 1.05 g (400.0 mmol) of CSM-P and 300 mL of dimethylformamide were charged, and 44.52 g (440.0 mmol) of triethylamine was added while stirring. Subsequently, the mixture was cooled to -10°C, and a solution of 38.46 g (200.0 mmol) of 1,6-naphthalenedithiol and 100.00 g of dimethylformamide was added dropwise, keeping the temperature below 0°C. The mixture was then stirred at 25°C for 12 hours. The mixture was then cooled to 15°C, and 4.17 g (40.0 mmol) of 35% hydrochloric acid was added at a temperature below 20°C. Insoluble matter was filtered off at room temperature, and the resulting filtrate was diluted with 600 mL of toluene, washed five times with 300 mL of water, and concentrated under reduced pressure to obtain 74.05 g of white crystals (yield: 87%).

[0168] The obtained white crystal 1 The H-NMR spectral data were as follows: · 1H-NMR (CDCl3) δ: 8.28 (d, 1H), 7.05-7.73 (m, 13H), 6.60-6.71 (m, 2H), 5.71 (dd, 1H), 5.67 (dd, 1H), 5.22 (d, 1H), 5.21 (dd, 1H), 4.21 (d, 2H), 4.10 (s, 2H). Furthermore, the IR spectral data of this white crystal was as shown in the chart in Figure 9. Based on these spectral data, the obtained white crystals were identified as a mixture of the compound represented by chemical formula (I-3-1), the compound represented by chemical formula (I-3-2), the compound represented by chemical formula (I-3-4), and the compound represented by chemical formula (I-3-7).

[0169] [Examples 10-18] The naphthalene compounds synthesized in Examples 1 to 9 were subjected to evaluation tests (measurement of refractive index), and the results obtained are shown in Table 3.

[0170] [Table 3]

[0171] Table 3 shows that all of the naphthalene compounds in Examples 1-9 exhibited high refractive indices. [Industrial applicability]

[0172] The naphthalene compound of the present invention is novel and has the characteristic of having a high refractive index. By polymerizing a composition containing this naphthalene compound, a cured product can be obtained that has excellent expandability, heat resistance, and mechanical strength, as well as a high refractive index. Therefore, the compositions of the present invention are suitable as materials used in the manufacture of coating materials, inks, adhesives, sealants, gas barrier films, color filters, optical films, optical lenses, and touch panels.

Claims

1. Naphthalene compounds represented by chemical formula (I-1), chemical formula (I-2), chemical formula (I-4), or chemical formula (I-5): 【Chemistry 1】 (In the formula, R １ These are identical and represent the base shown in formula (3). 【Chemistry 2】 (In the formula, Y １ (This represents a single bond or an alkylene group with 1 to 10 carbon atoms.) However, excluding 1,5-bis(allylthio)naphthalene, However, the naphthalene compound represented by chemical formula (I-4) is the same as the naphthalene compound represented by chemical formula (I-4-9). 【Transformation 3】

2. A method for synthesizing a naphthalene compound according to claim 1, A naphthalenedithiol compound represented by chemical formula (II-1), chemical formula (II-2), chemical formula (II-4), or chemical formula (II-5) is reacted with a dihaloalkane compound having 2 to 12 carbon atoms to haloalkylate two thiol groups (step 1). 【Chemistry 4】 The synthesis method is characterized by the subsequent reaction of the obtained compound with a base (second step).

3. A method for synthesizing a naphthalene compound represented by the chemical formula (I-3-12), 【Transformation 5】 The naphthalenedithiol compound represented by chemical formula (II-3) is reacted with a dihaloalkane compound selected from the group consisting of 1,2-dichloroethane, 1,2-dibromoethane, and 1,2-diiodoethane (step 1). 【Transformation 6】 The synthesis method is characterized by the subsequent reaction of the obtained compound with a base (second step).

4. A composition characterized by containing the naphthalene compound described in claim 1.

5. The naphthalene compound represented by the chemical formula (I-3-12), 【Transformation 7】 (i) Thiol compounds, and / or (ii) Photopolymerization initiator and / or thermal polymerization initiator A composition containing the following.

6. The naphthalene compound represented by the chemical formula (I-3-12), (i) Thiol compounds, and (ii) Photopolymerization initiator and / or thermal polymerization initiator The composition according to claim 5, comprising the above.

7. The composition according to claim 5, wherein the (i) thiol compound is at least one selected from the group consisting of aliphatic thiol compounds, aromatic thiol compounds, cyclic sulfide compounds, mercaptoalkyl sulfide compounds, mercaptopropionic acid esters, epoxy resin-terminated mercapto compounds, and mercaptoalkyl ether compounds.

8. A composition according to any one of claims 5 to 7, comprising an inorganic filler.

9. The composition according to claim 8, wherein the inorganic filler is at least one selected from the group consisting of zirconium oxide, titanium oxide, platinum, gold, diamond, silicon carbide, lithopone, silicon nitride, boron nitride, and aluminum nitride.

10. The composition according to any one of claims 5 to 7, comprising 0.1 to 100 parts by weight of the (i) thiol compound per 100 parts by weight of the naphthalene compound represented by the chemical formula (I-3-12).

11. The composition according to claim 5 or claim 6, comprising 0.1 to 20 parts by weight of the photopolymerization initiator in (ii) with respect to 100 parts by weight of the naphthalene compound represented by the chemical formula (I-3-12).

12. The composition according to claim 5 or claim 6, comprising 0.001 to 20% by weight of the thermal polymerization initiator in (ii) above, based on the total amount of the preceding composition.

13. The composition according to claim 8, wherein the inorganic filler is contained in a proportion of 0.01 to 85% by weight of the entire composition (total amount).

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