Naphthalene compound, method for synthesizing same, and resin composition containing said naphthalene compound

Abstract

The present invention provides a novel naphthalene compound, a method for synthesizing said naphthalene compound, and a resin composition containing said naphthalene compound. The resin composition according to the present invention can be applied to a coating material, an ink, an adhesive, a tackifier, a gas barrier film, a color filter, a prism, a diffraction grating, an optical mirror, an optical film, an optical lens, or the like. The present invention relates to a naphthalene compound represented by chemical formula (I), a method for synthesizing the same, a resin composition containing said compound, and a cured product thereof. (In the formula, Y represents a group selected from formulas (1) to (7). n represents an integer of 1 to 10.) (In formulas (1) to (7), m1 represents an integer of 1 to 3. m2 represents an integer of 1 to 2. The m3 are the same and represent an integer of 1 to 3. m4 represents an integer of 1 to 3.)

Description

Naphthalene compound, synthesis method thereof, and resin composition containing said naphthalene compound

[0001] The present invention relates to a novel naphthalene compound, a method for synthesizing the naphthalene compound, and a resin composition containing the naphthalene compound.

[0002] Conventionally, various materials have been used as resins for optical materials used as materials for various optical films, optical lenses, etc. Generally, polymers of polymerizable monomers that undergo polymerization in the presence of radical species are used for such materials, and for the purpose of improving light extraction efficiency, materials with high refractive indexes, such as sulfur-containing compounds and fluorene compounds having polymerizable functional groups, are considered suitable (e.g., Patent Documents 1 and 2). However, the resins for optical materials reported so far still have room for improvement in the low thermal expansion, heat resistance, mechanical strength, etc. of the cured products.

[0003] Furthermore, a naphthalene compound having both a naphthalene skeleton with a high refractive index and a sulfur element in the molecule is known, as disclosed in Patent Document 3. However, further improvements are required in terms of refractive index and compatibility with various solvents and resin components.

[0004] JP 2008-94987 A JP 2010-248358 A International Publication No. 2023 / 058449

[0005] An object of the present invention is to provide a novel naphthalene compound, a method for synthesizing the naphthalene compound, a resin composition containing the naphthalene compound, and a cured product thereof.

[0006] As a result of extensive research aimed at solving the above problems, the present inventors have found that the desired object can be achieved by a naphthalene compound obtained by reacting a certain type of dithiol compound with a certain type of bis(ethenylthio)naphthalene compound, and have thus completed the present invention. That is, the first invention is a naphthalene compound represented by chemical formula (I):

[0007] (In the formula, Y represents a group selected from formulas (1) to (7), and n represents an integer of 1 to 10.)

[0008] (In the formula, m1 represents an integer of 1 to 3. m2 represents an integer of 1 or 2. m3 is the same and represents an integer of 1 to 3. m4 represents an integer of 1 to 3.)

[0009] The second invention is a composition containing the naphthalene compound of the first invention and a bis(ethenylthio)naphthalene compound represented by chemical formula (III).

[0010] A third invention is a resin composition containing the naphthalene compound of the first invention or the composition of the second invention.

[0011] A fourth invention is the resin composition according to the third invention, which contains one member selected from the group consisting of a radical polymerization initiator, a cationic polymerization initiator, and a polysiloxane compound.

[0012] A fifth invention is a cured product of the resin composition of the third invention or the fourth invention.

[0013] The sixth invention is a method for synthesizing the naphthalene compound represented by chemical formula (I) of the first invention, characterized in that a dithiol compound represented by chemical formula (II) is reacted with a bis(ethenylthio)naphthalene compound represented by chemical formula (III). (In the formula, Y is the same as defined above.)

[0014] The naphthalene compound of the present invention is a novel compound characterized by a high refractive index. Because the naphthalene compound has two polymerizable groups in the molecule, it is expected to be useful as a material for optical applications. Furthermore, it is expected to have higher compatibility with various solvents and resin components than conventional materials for optical applications. The resin composition of the present invention is expected to give a cured product with a higher refractive index than conventional resin compositions. The resin composition of the present invention can be used in coating materials, inks, adhesives, pressure-sensitive adhesives, gas barrier films, color filters, prisms, diffraction gratings, optical mirrors, optical films, optical lenses, and the like.

[0015] The present invention will be described in detail below. 1. Naphthalene Compound 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").

[0016] In the naphthalene compound of the present invention, Y is preferably a group selected from formulae (1) to (3), and more preferably a group selected from formulae (1) and (2). n is preferably an integer of 1 to 9, and more preferably an integer of 1 to 8. m1 is preferably an integer of 1 to 2, and more preferably 1. m2 is preferably an integer of 1 to 2. m3 is preferably an integer of 1 to 2. m4 is preferably 1 or 3. The naphthalene compound of the present invention (naphthalene compound represented by chemical formula (I)) includes one compound selected from chemical formula (I) and a mixture of two or more compounds.

[0017] The naphthalene compounds represented by the chemical formula (I) include the naphthalene compounds represented by the chemical formulas (I-1) to (I-7).

[0018] (In the formula, n and m1 to m4 are the same as above.)

[0019] Examples of naphthalene compounds represented by chemical formula (I-1) include those represented by chemical formulas (I-1-1) to (I-1-16). 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-3-11). 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-5-11). Examples of the naphthalene compound represented by chemical formula (I-6) include those represented by chemical formulas (I-6-1) to (I-6-11). Examples of the naphthalene compound represented by chemical formula (I-7) include those represented by chemical formulas (I-7-1) to (I-7-11).

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] <Synthesis Method> The naphthalene compound of the present invention can be synthesized by reacting a dithiol compound represented by chemical formula (II) with a bis(ethenylthio)naphthalene compound represented by chemical formula (III) (see reaction scheme (A)).

[0037] (In the formula, Y and n are the same as defined above.)

[0038] The dithiol compound represented by the chemical formula (II) includes the dithiol compounds represented by the chemical formulas (II-1) to (II-7). The dithiol compound represented by chemical formula (II-1) is a precursor of the naphthalene compound represented by chemical formula (I-1), the dithiol compound represented by chemical formula (II-2) is a precursor of the naphthalene compound represented by chemical formula (I-2), the dithiol compound represented by chemical formula (II-3) is a precursor of the naphthalene compound represented by chemical formula (I-3), the dithiol compound represented by chemical formula (II-4) is a precursor of the naphthalene compound represented by chemical formula (I-4), the dithiol compound represented by chemical formula (II-5) is a precursor of the naphthalene compound represented by chemical formula (I-5), the dithiol compound represented by chemical formula (II-6) is a precursor of the naphthalene compound represented by chemical formula (I-6), and the dithiol compound represented by chemical formula (II-7) is a precursor of the naphthalene compound represented by chemical formula (I-7).

[0039] (In the formula, m1 to m4 are the same as above.)

[0040] Examples of dithiol compounds represented by chemical formula (II-1) include those represented by chemical formulas (II-1-1) to (II-1-5). Examples of dithiol compounds represented by chemical formula (II-2) include those represented by chemical formulas (II-2-1) to (II-2-6). Examples of dithiol compounds represented by chemical formula (II-3) include those represented by chemical formulas (II-3-1) to (II-3-3). Examples of dithiol compounds represented by chemical formula (II-5) include those represented by chemical formulas (II-5-1) to (II-5-3). Examples of dithiol compounds represented by chemical formula (II-6) include those represented by chemical formulas (II-6-1) to (II-6-3). Examples of the dithiol compound represented by the chemical formula (II-5) include the dithiol compounds represented by the chemical formulas (II-7-1) to (II-7-3).

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] The dithiol compound represented by chemical formula (II) can be purchased as a commercially available reagent and used, or can be synthesized in accordance with the methods described in, for example, WO 2023 / 176299, Tetrahedron (2007), 63(4), 927-933, etc.

[0048] The bis(ethenylthio)naphthalene compound represented by the chemical formula (III) includes bis(ethenylthio)naphthalene compounds represented by the chemical formulas (III-1) to (III-5).

[0049]

[0050] The bis(ethenylthio)naphthalene compound represented by the chemical formula (III) can be synthesized in accordance with the method described in WO 2023 / 058781.

[0051] The amounts (ratios) of the dithiol compound represented by chemical formula (II) and the bis(ethenylthio)naphthalene compound represented by chemical formula (III) used are not particularly limited. From the viewpoint of improving the yield of the naphthalene compound of the present invention (the naphthalene compound represented by chemical formula (I)), the amount (charge amount) of the bis(ethenylthio)naphthalene compound represented by chemical formula (III) used is usually in the range of 0.5 to 30 times, preferably 2 to 20 times, and more preferably 3 to 7 times the molar amount of the dithiol compound represented by chemical formula (II).

[0052] In carrying out this reaction, a radical initiator (i) may be used to promote the reaction, and a reaction solvent (ii) may be used to facilitate the reaction. Examples of the radical initiator (i) include azobisisobutyronitrile, t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionate).

[0053] The amount (charge amount) of the radical initiator (i) used is preferably in the range of 0.0001 to 1 mole relative to the amount (charge amount) of the dithiol compound represented by the chemical formula (II).

[0054] Examples of the reaction solvent (ii) include water, methanol, ethanol, propanol, 2-propanol, butanol, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, etc. The reaction solvent (ii) may be used alone or in combination of two or more thereof.

[0055] In this reaction, the reaction temperature is preferably set in the range of 30 to 120° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 24 hours.

[0056] In this synthesis method, in addition to the compound represented by chemical formula (I), a compound having a cyclic structure (a compound represented by chemical formula (IV-1)), a compound having an ethenylthio group and a thiol group at both ends (a compound represented by chemical formula (IV-2)), or a compound having thiol groups at both ends (a compound represented by chemical formula (IV-3)) can be obtained from the dithiol compound represented by chemical formula (II) and the bis(ethenylthio)naphthalene compound represented by chemical formula (III).

[0057] (In the formula, Y is the same as defined above, and r represents an integer of 0 to 9.)

[0058] Examples of compounds represented by chemical formula (IV-1) include compounds represented by chemical formulas (IV-1-1) to (IV-1-9). Examples of compounds represented by chemical formula (IV-2) include compounds represented by chemical formulas (IV-2-1) to (IV-2-12). Examples of compounds represented by chemical formula (IV-3) include compounds represented by chemical formulas (IV-3-1) to (IV-3-12).

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067] After completion of the reaction, the reaction mixture can be isolated from the resulting reaction mixture by, for example, concentrating the reaction mixture by distilling off the reaction solvent, solvent extraction, etc. If necessary, the reaction mixture can be purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.

[0068] Furthermore, the compound represented by chemical formula (I), the raw materials, and / or the by-products can be separated or purified from the reaction mixture, if necessary, by using means such as washing with water or the like, treatment with activated carbon, silica gel chromatography, or recrystallization.

[0069] This synthesis method makes it possible to obtain a mixture (composition) containing the compound represented by chemical formula (I), and, if necessary, raw materials (dithiol compounds represented by chemical formula (II) and / or bis(ethenylthio)naphthalene compounds represented by chemical formula (III)), by-products (one or more compounds selected from chemical formulas (IV-1), (IV-2), and (IV-3)), etc. This is sometimes referred to as the "composition of the present invention."

[0070] That is, one embodiment of the product obtained by this synthesis method is a mixture (composition) containing the compound represented by chemical formula (I) and raw materials (a dithiol compound represented by chemical formula (II) and / or a bis(ethenylthio)naphthalene compound represented by chemical formula (III)). Another embodiment is a mixture (composition) containing the compound represented by chemical formula (I) and the bis(ethenylthio)naphthalene compound represented by chemical formula (III). Another embodiment is a compound represented by chemical formula (I) or a mixture (composition) containing the compound.

[0071] The product is typically a mixture (composition) containing a compound represented by chemical formula (I) and a bis(ethenylthio)naphthalene compound represented by chemical formula (III). In this case, the content of the compound represented by chemical formula (I) relative to the total content of the compound represented by chemical formula (I) and the bis(ethenylthio)naphthalene compound represented by chemical formula (III) in the mixture is typically 10 to 80%, preferably 20 to 70%, more preferably 25 to 65%, and particularly preferably 30 to 60%. This content ratio can be calculated from the peak area ratio of the two compounds when the mixture is analyzed by gel permeation chromatography. For specific details, see the Examples section.

[0072] 2. Resin Composition Containing Naphthalene Compound The present invention also provides a resin composition containing the naphthalene compound of the present invention (a compound represented by chemical formula (I)), as well as a resin composition containing the composition of the present invention. Hereinafter, this may be referred to as the "resin composition of the present invention." The resin composition of the present invention contains the naphthalene compound of the present invention (hereinafter, may be referred to as the "first curable compound") as an essential component. The naphthalene compound of the present invention means one compound or a mixture of two or more compounds selected from the compounds represented by chemical formula (I).

[0073] As explained in the section 1. <Synthesis Method> above, the product obtained by the synthesis reaction includes various embodiments. Typically, the product contains the naphthalene compound of the present invention and a raw material (a bis(ethenylthio)naphthalene compound represented by chemical formula (III)), etc. This product can be used as the resin composition of the present invention, or can be contained in the resin composition of the present invention. Alternatively, the naphthalene compound of the present invention can be isolated or purified from this product and then contained in the resin composition of the present invention.

[0074] The content of the naphthalene compound of the present invention in the resin composition of the present invention is usually 0.001 to 100% by weight, preferably 0.001% by weight or more but less than 100% by weight, even more preferably 1% by weight or more, and particularly preferably 10% by weight or more but less than 90% by weight.

[0075] Because the naphthalene compound of the present invention has a carbon-carbon double bond in its molecule, it can be polymerized to obtain a cured product. By allowing a curable compound other than the naphthalene compound of the present invention to coexist during this polymerization, a cured product can be obtained in which the naphthalene compound of the present invention and the other curable compound are copolymerized. Because the resin composition of the present invention contains this naphthalene compound, it can also be referred to as a polymerizable composition or a curable composition. Examples of the other curable compound include an ene compound having a carbon-carbon double bond in its molecule (hereinafter sometimes referred to as a "second curable compound"), a compound having an epoxy group, an oxetane ring, or a vinyl group in its molecule (hereinafter sometimes referred to as a "third curable compound"), and a polysiloxane compound (hereinafter sometimes referred to as a "fourth curable compound").

[0076] (First Resin Composition) The first resin composition of the present invention contains, as essential components, the naphthalene compound of the present invention (or the composition of the present invention) and a radical polymerization initiator (a photoradical polymerization initiator and / or a thermal radical polymerization initiator), and optionally contains a second curable compound (an ene compound having a carbon-carbon double bond in the molecule). The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

[0077] Examples of the polymerizable monomer include (1) (meth)acrylic acid alkyl ester monomers, (2) hydroxyl group-containing monomers, (3) carboxyl group-containing monomers, (4) amino group-containing monomers, (5) acetoacetyl group-containing monomers, (6) isocyanate group-containing monomers, (7) glycidyl group-containing monomers, (8) monomers 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, and (13) polyfunctional unsaturated compounds.

[0078] (1) Examples of (meth)acrylic acid alkyl ester monomers 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, and polyisobornyl (meth)acrylate.

[0079] (2) Examples of hydroxyl group-containing monomers include (meth)acrylic acid hydroxyalkyl esters 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 others such as 2-acryloyloxyethyl 2-hydroxyethyl acrylate. Examples of the monomers include primary hydroxyl group-containing monomers such as taric acid, N-methylol (meth)acrylamide, and hydroxyethyl acrylamide; secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro 2-hydroxypropyl (meth)acrylate, propylene glycol diglycidyl ether-epoxy di(meth)acrylate, phenol glycidyl ether-epoxy (meth)acrylate, and bisphenol A diglycidyl ether-epoxy di(meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate.

[0080] (3) Examples of carboxyl group-containing monomers include (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, and cinnamic acid.

[0081] (4) Examples of amino group-containing monomers include tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate.

[0082] (5) Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0083] (6) Examples of isocyanate group-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0084] (7) Examples of glycidyl group-containing monomers include, in addition to 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, 1,3,5-tris(2,3-epoxypropyl)isocyanurate-(meth)acrylate, and other epoxy (meth)acrylates which are reaction products of epoxy compounds with (meth)acrylic acid, and glycidyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0085] (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, and vinylnaphthalene.

[0086] (9) Examples of monomers containing an alkoxy group and an oxyalkylene group 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, and stearoxypolyethylene glycol mono(meth)acrylate.

[0087] (10) Examples of alkoxyalkyl(meth)acrylamide monomers include methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, isopropoxymethyl(meth)acrylamide, n-butoxymethyl(meth)acrylamide, and isobutoxymethyl(meth)acrylamide.

[0088] (11) Examples of (meth)acrylamide monomers include (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and (meth)acrylamide N-methylol(meth)acrylamide.

[0089] (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 biphenyloxypolyalkylene glycol (meth)acrylates include (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.

[0090] (13) Examples of polyfunctional unsaturated compounds include bifunctional monomers, trifunctional or higher functional monomers, urethane (meth)acrylates, polyurethane (meth)acrylates, thiourethane (meth)acrylates, polythiourethane (meth)acrylates, the above-mentioned epoxy (meth)acrylates, ester (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, (meth)acrylates having a cardo structure, sulfur-containing (meth)acrylates, and vinyl thioethers.

[0091] Specific examples of bifunctional 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 di(meth)acrylate, and propylene oxide. Examples of the di(meth)acrylate include modified bisphenol A 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, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0092] Specific examples of tri- or higher functional monomers 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 polyglycerin. Examples of the polyisocyanurate include diethyl ether poly(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene oxide-modified isocyanuric acid 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, and succinic acid-modified pentaerythritol tri(meth)acrylate.

[0093] Specific examples of (meth)acrylates having a cardo structure include compounds represented by chemical formula (V).

[0094] (In the formula, R １ and R ２ are the same or different and represent a hydrogen atom or a methyl group; and a are the same or different and represent an integer of 1 to 4.

[0095] Specific examples of sulfur-containing (meth)acrylates include compounds represented by chemical formula (VI).

[0096] (In the formula, R ３ are the same or different and represent an alkyl group having 1 to 5 carbon atoms. ４ are the same or different and represent a hydrogen atom or a methyl group; b are the same or different and represent 0 or 1.

[0097] In addition to the above-mentioned polymerizable monomers, divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyltoluene, vinylpyridine, vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl Examples of the ester include ketone, 2-chloroethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluril, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid triallyl 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 (for example, (3-vinylbenzyl)-2-thiophenecarboxylate, (4-vinylbenzyl)-2-thiophenecarboxylate, etc.).

[0098] The first resin composition of the present invention contains the naphthalene compound of the present invention as an essential component and, if necessary, the second curable compound described above. As the second curable compound, a combination of the polymerizable monomer and polymerizable oligomer described above may be used. As the polymerizable monomer, a combination of the polymerizable monomers exemplified above may be used (different types of polymerizable monomers may be used in combination), and as the polymerizable oligomer, a combination of different types of polymerizable oligomers may also be used. Regarding the respective contents of the naphthalene compound of the present invention and the second curable compound in the first resin composition of the present invention, the content of the second curable compound is preferably in the range of 0 to 1,000 times (weight ratio), and more preferably in the range of 0.01 to 100 times (weight ratio), the content of the naphthalene compound of the present invention.

[0099] The first resin composition of the present invention may contain a thiol compound as a curing agent.Examples of the thiol compound include aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-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 compounds represented by the chemical formula ( VII) cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds; mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; mercaptopropionic acid esters such as trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate); epoxy resin terminal mercapto compounds; 3,6-dioxa-1,8-octanedithiol, pentaerythritol triporpanethiol, 1,2,3-(3-mercaptopropyloxy)propane, mercaptoalkyl ether disulfide compounds represented by chemical formula (VIII), 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-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol mercaptoalkyl ether compounds such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, and the like; 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril; and these may be used in combination.

[0100] (In the formula, p represents an integer of 1 to 5.)

[0101] (In the formula, q represents an integer of 1 to 20.)

[0102] In the first resin 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, relative to 100 parts by weight of the curable compounds (the total of the first curable compound and the second curable compound).

[0103] The first resin composition of the present invention may contain a reactive diluent. In this specification, the reactive diluent refers to 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, in addition to the epoxy group, other polymerizable functional groups, such as alkenyl groups such as vinyl and allyl, or unsaturated carboxylic acid residues such as acryloyl and methacryloyl.

[0104] Examples of the reactive diluent include monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0105] The content of the reactive diluent in the first resin composition of the present invention is preferably 1 to 400 parts by weight per 100 parts by weight of the curable compounds (the total of the first curable compound and the second curable compound).

[0106] Methods for polymerizing (curing) the first resin composition of the present invention include photocuring and thermal curing. Photocuring methods include a method of irradiating with active energy rays, preferably a method in which a photoradical polymerization initiator is used in combination. 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 the light source, for example, an ultra-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. Furthermore, light sources such as lasers and LEDs that are capable of emitting light of various wavelengths, which have become increasingly popular in recent years, may also be used. The irradiation dose of active energy rays can be appropriately set depending on the type of light source, etc.

[0107] The photo-radical polymerization initiator can be contained in the resin composition. In addition, in order to improve production efficiency and the properties of the cured product, thermal polymerization (thermal curing) may be used in combination with the photo-curing.

[0108] The photoradical polymerization initiator can be any commonly used photoradical polymerization initiator without any particular limitation. Examples of the photoradical polymerization initiator include 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-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzo benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, hydroxybenzophenone, methyl o-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-oxo-1,2-dimethylphenyl)benzoyl]benzophenone, benzoin derivatives such as benzoin isopropyl ether and benzoin isobutyl ether; benzophenones such as (4-benzoylbenzyl)trimethylammonium chloride, (4-benzoylbenzyl)trimethylammonium 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 of such compounds include acylphosphonoxides 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 methylphenyl glyoxylate. These compounds may be used alone or in combination of two or more.

[0109] In the first resin composition of the present invention, the content of the photoradical polymerization 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, relative to 100 parts by weight of the curable compounds (the total of the first curable compound and the second curable compound).

[0110] The first resin composition of the present invention may also contain an auxiliary for the photoradical polymerization initiator, such as triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's 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.

[0111] In addition, the first resin 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, benzil, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, 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 the like.

[0112] In the first resin composition of the present invention, the content of the sensitizer is, for example, 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, relative to 100 parts by weight of the curable compounds (the total of the first curable compound and the second curable compound).

[0113] On the other hand, a method for thermally curing the first resin composition of the present invention can include a method in which a thermal radical polymerization initiator is used in combination. The thermal radical polymerization initiator may be contained in the resin composition. The thermal curing conditions, such as the heating temperature and heating time, can be set appropriately, but are preferably set 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. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a sealed curing oven or a tunnel oven capable of continuous curing can be used as the curing device.

[0114] As the thermal radical polymerization initiator, any commonly used one can be used without any particular limitation, and examples thereof include 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, and t-butyl peroxyneodecanoate. peroxides such as benzoyl peroxide, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 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.

[0115] The content of the thermal radical polymerization initiator in the first resin composition of the present invention is preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight, based on the entire resin composition (total amount).

[0116] The first resin composition of the present invention may further contain, as long as the effects of the present invention are not impaired, 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, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, silica powder such as spherical silica, spherical alumina, Oxides such as crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, etc.; nitrides such as boron nitride, silicon nitride, aluminum nitride, etc.; carbides such as silicon carbide, hydroxides such as aluminum hydroxide, magnesium hydroxide, etc.; metals and alloys such as copper, silver, iron, aluminum, nickel, titanium, platinum, gold, etc.; diamond, carbonaceous materials such as carbon, etc.); thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density, and low-density polyethylenes, polypropylene, polybutene, and polypentene, etc.) polymers, ethylene-propylene copolymers, polyamide resins such as nylon-6 and nylon-6,6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylic resins (including curable compounds other than the above-mentioned polymerizable monomers), acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), epoxy resins (epoxy compounds), silicone resins, fluorine-based resins, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers, etc.); reinforcing agents (glass fiber, carbon fiber, etc.); anti-sagging agents (hydrogenated castor oil, fine particle silicic anhydride, etc.); matting agents (fine powder silica, paraffin wax, etc.); abrasives (zinc stearate, etc.); internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.);It may contain additives (modifiers) such as diluents (organic solvents such as n-butyl alcohol, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and 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)); surfactants, leveling agents, antifoaming agents, fragrances, flame retardants, and dyes;

[0117] The thermoplastic resins and thermosetting resins include resins (compounds) having a cardo structure (a skeletal structure in which four aromatic rings are bonded to a carbon atom), as represented by chemical formula (IX).

[0118] (In the formula, c represents the degree of polymerization.)

[0119] Examples of compounds having a cardo structure include monomers such as 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.

[0120] In the first resin composition of the present invention, the content of the additive (modifier) ​​may be 0.01 to 85% by weight based on the entire resin composition (total amount).

[0121] Table 1 shows preferred blending examples (excluding organic solvents) in the first resin composition of the present invention.

[0122]

[0123] The method for preparing the first resin composition of the present invention is not particularly limited, and the first resin composition can be prepared, for example, by mixing the naphthalene compound of the present invention with the second curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier), or by mixing a solution in which the naphthalene compound of the present invention is dissolved or dispersed in a diluent (organic solvent) and / or a reactive diluent with the second curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier). Known methods can be used as the mixing means.

[0124] (Second Resin Composition) The second resin composition of the present invention contains, as essential components, the naphthalene compound of the present invention (or the composition of the present invention) and a cationic polymerization initiator (a photocationic polymerization initiator and / or a thermal cationic polymerization initiator), and optionally contains a third curable compound (a compound having an epoxy group, an oxetane ring, an episulfide group, or a vinyl group in the molecule). The third curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

[0125] Examples of the polymerizable monomer include known epoxy compounds (note: sometimes referred to as epoxy resins), oxetane compounds, epoxy-oxetane compounds (having an oxirane ring and an oxetane ring in the molecule), episulfide compounds, vinyl-based monomers, etc.

[0126] The epoxy compound can be used without any particular limitation as long as it has an oxirane ring (epoxy group / glycidyl group) in the molecule. Examples include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl glycoluril compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; 3 Examples of epoxy compounds 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, epoxy-modified phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, cycloaliphatic epoxy resins, and urethane-modified epoxy resins, as well as epoxy-modified organopolysiloxane compounds obtained by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having a SiH group (for example, the epoxy-modified organopolysiloxane compounds disclosed in JP-A-2004-99751 and JP-A-2006-282988). These may also be used in combination.

[0127] The oxetane compound can be used without any particular limitation as long as it has an oxetane ring (oxetanyl group / oxetane group) in the molecule, and examples thereof include 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, 4-methyl ... (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl ... ter, 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, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl)ether, trimethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 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 hexafluorophosphate 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 (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, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, etc.

[0128] Any epoxy-oxetane compound can be used without particular limitation as long as it has an oxirane ring (ibid.) and an oxetane ring (ibid.) in the molecule, and examples thereof include those described in U.S. Pat. No. 3,457,193, JP-A No. 2005-002191, JP-A No. 2007-270070, JP-A No. 2010-111713, and JP-A No. 2011-208089. The epoxy-oxetane compounds described in these documents are incorporated by reference into the disclosure of this specification.

[0129] The episulfide compound can be any compound having an episulfide group in the molecule, and examples thereof include episulfide compounds obtained by episulfidating part or all of the epoxy groups of the above-mentioned epoxy compounds. Other examples include thiiranemethanethiol, 2,2'-bis[9H-fluoren-9-ylidenebis(6,2-phenyleneoxymethylene)]thiirane, 2,2'-bis[9H-fluoren-9-ylidenebis(6,2-naphthyleneoxymethylene)]thiirane, and episulfide compounds having an unsaturated group such as vinylphenyl thioglycidyl ether, vinylbenzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, and allyl thioglycidyl ether.

[0130] The vinyl monomer may be any vinyl monomer capable of cationic polymerization, and examples thereof include styrenes, alkenyl ethers, indene, and N-vinylcarbazole. Preferred are styrenes and alkenyl ethers. Examples of styrenes include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene. Examples of alkenyl ethers include 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]octyl vinyl ether. ２，６ cycloalkyl vinyl ethers such as 1-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.

[0131] The second resin composition of the present invention contains the naphthalene compound of the present invention as an essential component and, if necessary, the third curable compound described above. As this third curable compound, a combination of the polymerizable monomer and polymerizable oligomer described above may be used. As the polymerizable monomer, a combination of the polymerizable monomers exemplified above may be used (different types of polymerizable monomers may be used in combination), and as the polymerizable oligomer, a combination of different types of polymerizable oligomers may also be used. Regarding the respective contents of the naphthalene compound of the present invention and the third curable compound in the second resin composition of the present invention, the content of the third curable compound is preferably in the range of 0 to 1,000 times (weight ratio), and more preferably in the range of 0.01 to 100 times (weight ratio), the content of the naphthalene compound of the present invention.

[0132] Methods for polymerizing (curing) the second resin composition of the present invention include photocuring and thermal curing. Photocuring methods include a method of irradiating with active energy rays, preferably a method in which a cationic polymerization initiator is used in combination. 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 the light source, for example, an ultra-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. Furthermore, light sources such as lasers and LEDs that are capable of emitting light of various wavelengths, which have become increasingly popular in recent years, may also be used. The dose of active energy rays can be appropriately set depending on the type of light source, etc.

[0133] The photocationic polymerization initiator may be contained in the resin composition. In addition, in order to improve production efficiency and the properties of the cured product, heat curing may be used in combination with photocuring.

[0134] The cationic photopolymerization initiator may be any commonly used one without any particular limitation, and examples thereof include onium salts and organometallic complexes. The cationic photopolymerization initiator may be any of those described in the section on the first resin composition. The content of the cationic photopolymerization initiator in the second resin composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0135] When the second resin composition of the present invention is photocured, the sensitizer described in the section on the first resin composition can be used.

[0136] On the other hand, when thermally curing the second resin composition of the present invention, a thermal cationic polymerization initiator can be used, and this can be contained in the resin composition. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a sealed curing oven or a tunnel oven capable of continuous curing can be used as the curing device. The heating (curing) temperature and heating (curing) time can be appropriately set taking into consideration the composition and shape (thickness) of the resin composition to be irradiated.

[0137] The thermal cationic polymerization initiator may be any commonly used one without particular limitation, and examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes. The thermal cationic polymerization initiator may be any of those described in the section on the first resin composition. The content of the thermal cationic polymerization initiator in the second resin composition of the present invention is preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight.

[0138] The second resin composition of the present invention may further contain, as necessary, the additives (modifiers) described in the section on the first resin composition in an amount of 0.01 to 85% by weight based on the entire second resin composition (total amount), as long as the effects of the present invention are not impaired.

[0139] Table 2 shows preferred examples of the blending of the second resin composition of the present invention (excluding the organic solvent).

[0140]

[0141] The method for preparing the second resin composition of the present invention is not particularly limited, and the composition can be prepared by measuring out predetermined amounts of the above-mentioned components and stirring and mixing them. For example, the composition can be prepared by premixing, followed by mixing or melt-kneading using a roll mixer, kneader, extruder, or the like. If necessary, an organic solvent (a viscosity-adjusting diluent) may be used.

[0142] (Third Resin Composition) The third resin composition of the present invention contains the naphthalene compound of the present invention (or the composition of the present invention) as an essential component, and also contains a fourth curable compound (polysiloxane compound). The fourth curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

[0143] The polysiloxane compound is not particularly limited as long as it is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) in one molecule and a polysiloxane structure as the main chain.

[0144] The polysiloxane compound preferably has 2 to 200 hydrogen atoms bonded to silicon atoms in one molecule, and more preferably 3 to 100. Examples of the molecular structure of the polysiloxane compound include a linear, branched, cyclic, and three-dimensional network structure.

[0145] In polysiloxanes, the bonding positions of the hydrogen atoms bonded to silicon atoms can be, for example, either or both of the terminals and side chains of the polysiloxane molecular chain, or can be either or both of the terminals of the polysiloxane molecular chain.

[0146] The polysiloxane compound may be, for example, an organohydrogenpolysiloxane represented by the average composition formula (X).

[0147] (In the formula, R ５independently represent an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds. d and e represent numbers satisfying the conditions 0<d<2, 0.8≦e≦2, and 0.8<d+e≦3, and preferably satisfy the conditions 0.05≦d≦1, 0.9≦e≦2, and 1.0≦d+e≦2.7. The number of silicon atoms in one molecule is 2 to 300, and preferably 3 to 200.

[0148] R in this average composition formula (X) ５ Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. Of these, from the viewpoints of heat resistance and light resistance, lower alkyl groups having 1 to 3 carbon atoms such as methyl, phenyl, and 3,3,3-trifluoropropyl are preferred.

[0149] Examples of polysiloxane compounds include methylhydrogenpolysiloxanes capped at both molecular chain terminals with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, methylhydrogenpolysiloxanes capped at both molecular chain terminals with silanol groups, dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular chain terminals with silanol groups, dimethylpolysiloxanes capped at both molecular chain terminals with dimethylhydrogensiloxy groups, methylhydrogenpolysiloxanes capped at both molecular chain terminals with dimethylhydrogensiloxy groups, and dimethylsiloxane-methylhydrogensiloxane copolymers capped at both molecular chain terminals with dimethylhydrogensiloxy groups; (R ５ ) ２ HSiO １／２ Units and SiO ４／２ units, and optionally (R ５ ) ３ SiO １／２ Units, (R ５ ) ２ SiO ２／２ Unit, R ５ HSiO ２／２ Units: (H)SiO３／２ Unit or R ５ SiO ３／２ Silicone resins that may contain units (wherein R ５ is R appearing in the average composition formula (X) ５ In addition to the above-exemplified compounds, examples include those in which some or all of the methyl groups have been substituted with other alkyl groups such as ethyl groups and propyl groups, phenyl groups, or hydrosilyl groups.

[0150] Examples of the polysiloxane compound include organohydrogenpolysiloxanes represented by the chemical formulas (XI-1) to (XI-4).

[0151] (In the formula, R ５ is R appearing in the average composition formula (X) ５ where f represents 0 or an integer of 1 or more, g represents an integer of 1 or more, and h represents an integer of 2 or more.

[0152] The polysiloxane compounds can be used alone or in combination of two or more.

[0153] The polysiloxane compound can be prepared by a conventionally known method. For example, a polysiloxane compound represented by the chemical formula: ５ SiHCl ２ and (R ５ ) ２ SiHCl (wherein R ５ is R appearing in the average composition formula (X) ５ or a compound having the formula: (R ５ ) ３ SiCl and (R ５ ) ２ SiCl ２ (In the formula, R ５ is R appearing in the average composition formula (X) ５ The polysiloxane compound can be obtained by co-hydrolyzing at least one chlorosilane selected from the group consisting of chlorosilanes (similar to the above). The polysiloxane compound can also be obtained by equilibrating the polysiloxane obtained by co-hydrolysis.

[0154] With regard to the respective contents of the naphthalene compound of the present invention and the fourth curable compound in the third resin composition of the present invention, the content of the fourth curable compound is preferably in the range of 0 to 1,000 times (weight ratio) the content of the naphthalene compound of the present invention, and more preferably in the range of 0.01 to 100 times (weight ratio).

[0155] The third resin composition of the present invention may contain a reaction catalyst to promote the addition reaction between the carbon-carbon double bond of the naphthalene compound of the present invention and the hydrogen atom (SiH group) bonded to the silicon atom of the polysiloxane compound. By containing the reaction catalyst, a resin composition with excellent curability can be obtained.

[0156] As the reaction catalyst, a conventionally known hydrosilylation reaction catalyst can be used. For example, platinum group metals such as platinum (including platinum black), rhodium, and palladium; ２ PtCl ４ ・n １ H ２ O, H ２ PtCl ６ ・n １ H ２ O, NaHPtCl ６ ・n １ H ２ O, KHPtCl ６ ・n １ H ２ O, Na ２ PtCl ６ ・n １ H ２ O.K. ２ PtCl ４ ・n １ H ２ O, PtCl ４ ・n １ H ２ O, PtCl ２ , Na ２ HPtCl ４ ・n １ H ２ O (in the formula, n １is an integer of 0 to 6, preferably 0 or 6); alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid with olefins (see U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metal catalysts such as platinum black and palladium supported on a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (Wilkinson's catalyst); and complexes of platinum chloride, chloroplatinic acid, or chloroplatinic acid with vinyl group-containing siloxanes, particularly vinyl group-containing cyclic siloxanes.

[0157] In the third resin composition of the present invention, the content of the reaction catalyst is, for example, from the viewpoint of exhibiting excellent curability, preferably 0.1 to 500 ppm, and more preferably 10 to 100 ppm, in terms of the weight of platinum group metal, relative to the total amount of the curable compounds (the sum of the first curable compound and the fourth curable compound).

[0158] The third resin composition of the present invention may further contain, as necessary, the additives (modifiers) described in the section on the first resin composition in an amount of 0.01 to 85% by weight based on the entire third resin composition (total amount), as long as the effects of the present invention are not impaired.

[0159] Methods for polymerizing (curing) the third resin composition of the present invention include photocuring and thermal curing. Photocuring methods include irradiation with active energy rays. 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 the light source, for example, an ultra-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. Furthermore, light sources such as lasers and LEDs that are capable of emitting light of various wavelengths, which have become increasingly popular in recent years, may also be used. The dose of active energy rays can be appropriately set depending on the type of light source, etc.

[0160] As conditions for thermally curing the third resin composition of the present invention, from the viewpoints of excellent curability, allowing the curing time and pot life to be of appropriate lengths, suppressing foaming, suppressing cracking in the cured product, and achieving excellent smoothness, moldability, and physical properties in the cured product, the heating temperature can be set to typically 100° C. or higher, preferably 120° C. or higher, more preferably in the range of 120 to 200° C., and even more preferably in the range of 120 to 180° C. The heating time is adjusted appropriately by setting the heating temperature, but can be set preferably within 20 hours, more preferably within 12 hours.

[0161] The method for preparing the third resin composition of the present invention is not particularly limited, and the composition can be prepared by measuring out predetermined amounts of the above-mentioned components and mixing them with stirring. The third resin composition of the present invention can be a one-component or two-component type.

[0162] When the third resin composition of the present invention is a two-component type, it can be prepared by separating into a first component containing a polysiloxane compound and a curing catalyst and a second component containing the naphthalene compound of the present invention. The additive (modifier) ​​can be added to either or both of the first and second components.

[0163] With regard to the third resin composition of the present invention, from the viewpoint of pot life, after mixing a liquid containing components other than the polysiloxane compound with a liquid containing the polysiloxane compound, the viscosity after 24 hours at 23°C is preferably 5 to 10,000 mPa s, and more preferably 5 to 5,000 mPa s (E-type viscometer, 23°C / humidity 55%).

[0164] 3. Applications The resin composition of the present invention (hereinafter, including the "first resin composition," "second resin composition," and "third resin composition") contains the naphthalene compound of the present invention, and therefore can provide a cured product with a high refractive index. Therefore, the resin composition of the present invention is suitable as a material used in producing coating materials, inks, adhesives, pressure-sensitive adhesives, gas barrier films, color filters, optical films, optical lenses, touch panels, etc.

[0165] Examples of applications of the 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 materials, wall materials, artificial marble, etc.).

[0166] Examples of the ink include color ink, printing ink, UV ink, inkjet ink, etc. These inks are used for offset printing, flexographic printing, gravure printing, screen printing, inkjet printing, etc.

[0167] The adhesives can be used for semiconductors, optics, optical components, optical waveguide coupling, fixing peripheral members of optical waveguides, and bonding CDs / DVDs.

[0168] The adhesives can be used for adhesive tapes, adhesive sheets, adhesive labels, and the like.

[0169] The gas barrier film can be used in electronic paper, flexible displays, organic EL devices, organic solar cells, and the like.

[0170] The applications of the color filters include color liquid crystal displays (color filter on array (COA)), color imaging devices, organic EL displays, and the like.

[0171] Examples of the optical film include protective films for polarizing plates, films for liquid crystal display devices such as support films for prism sheets and light-guiding films, functional films such as hard coat films, 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.

[0172] Examples of the optical lens include lenses for microscopes, endoscopes, telescopes, cameras, eyeglasses, and the like, optical cover lenses, gradient index lenses, Fresnel lenses, lenses for smart glasses, lenticular lenses, VR lenses, AR lenses, lenses for laser beam printers, lenses for sensors, prism lenses, and pickup lenses for optical discs.

[0173] The touch panel can be used in personal computers, car navigation systems, mobile phones, electronic dictionaries, office automation and factory automation equipment, and the like.

[0174] The resin composition of the present invention can be further used in a variety of applications, including transparent materials, high refractive index layers of anti-reflection films, optical thin films such as reflectors, core materials and cladding materials for optical fibers, optical waveguides, holograms, and other optical materials, dicing tapes, insulating materials (wire coatings, etc.), solder resist inks, printed wiring boards, copper-clad laminates, resin-coated copper foils, prepregs, high-voltage insulating materials, interlayer insulating materials, TFT passivation films, TFT gate insulating films, TFT interlayer insulating films, TFT transparent planarizing films, insulating packings, insulating coating materials, paints, UV powder paints, molding materials (sheets, films, FRP, etc.), sealants, liquid crystal sealants, display device sealants, high-heat-resistant sealants, potting materials, encapsulants (semiconductor encapsulants, electrical material encapsulants, organic EL and LED element encapsulants, and various solar cell encapsulants), resist materials (liquid resists), and the like. The materials are expected to be used in electrical and electronic applications such as photoresists, color resists, dry film resists, solder resists, color filter resists, photospacer materials for liquid crystal cells, stereolithography, solar cell materials, fuel cell materials, display materials, recording materials, photosensitive drums for copiers, liquid crystal displays, microdisplays, light guide plates for liquid crystal displays, microlens arrays, Fresnel rhomb wave plates, polarizing beam splitters, and solid electrolytes for batteries, as well as raw materials and components for vibration-proofing materials, waterproofing materials, moisture-proofing materials, heat-shrinkable rubber tubing, O-rings, gas separation membranes, concrete protective materials, linings, soil injection agents, cold and heat storage materials, sealing materials for sterilization treatment equipment, and oxygen-permeable membranes, and as additives (modifiers) to be blended with other resins or resin compositions (thermoplastic, thermosetting, photosetting).

[0175] [Main raw materials and reagents] 1,6-Naphthalenedithiol (manufactured by Sugai Chemical Industry Co., Ltd.; see chemical formula (II-1-3)) 4,4'-Thiobisbenzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.; see chemical formula (II-2-1)) 1,6-Bis(ethenylthio)naphthalene (synthesized in accordance with the method described in WO 2023 / 058781; see chemical formula (III-3)) Toluene (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) Ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) 1,3,4,6-Tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0176] The evaluation test (measurement of refractive index) employed in the examples and comparative examples was carried out as follows.

[0177] [Measurement of Refractive Index] The refractive index (25°C) of the products (reaction mixtures) obtained in Examples 1 to 5, the compound of Comparative Example 1, and the cured films obtained in Example 6 and Comparative Example 2 under LED light (D-line wavelength) was measured using an Abbe refractometer (Atago Co., Ltd., "Multi-wavelength Abbe refractometer DR-M4") in accordance with JIS K 0062 ("Method for measuring the refractive index of chemical products"). Of the products obtained in Examples 1 to 5, the refractive index (25°C) of the slurry-like products (products of Examples 3 and 4) was measured using the following method. (1) Three measurement samples with different concentrations were prepared by dissolving the product in 1-methyl-2-pyrrolidone (NMP) to give slurry concentrations of 60, 70, and 80% by weight. (2) The refractive index (25°C) of the prepared measurement samples under LED light (D-line wavelength) was measured using an Abbe refractometer (Atago Co., Ltd., "N Multi-wavelength Abbe refractometer DR-M4"). (3) A calibration curve was prepared from the obtained measured values, and the refractive index at a slurry concentration of 100% by weight was calculated, which was taken as the refractive index of the slurry.

[0178] Example 1 Synthesis of Naphthalene Compound Represented by Chemical Formula (I-1) 3.00 g (12.3 mmol) of 1,6-bis(ethenylthio)naphthalene and 12.00 g of toluene were placed in a 50 mL flask, and 0.35 g (1.8 mmol) of 1,6-naphthalenedithiol dissolved in 0.35 g of toluene was added dropwise while stirring at 60°C. The mixture was then stirred at 60°C for 3 hours. The mixture was then cooled to room temperature and concentrated under reduced pressure to obtain 3.34 g of a pale yellow liquid.

[0179] The resulting pale yellow liquid １ H-NMR chart (CDCl ３) A signal derived from ethylene chains was observed at 3.06-3.24 ppm. The resulting pale yellow liquid was also analyzed by gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 x 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 x 300 mm, 3.0 μm x 2), detector: PDA (210 nm)). It was confirmed that the pale yellow liquid contained 1,6-bis(ethenylthio)naphthalene as the main component (peak at 37.4 minutes elution time), and further contained a naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 (peak at 26.3 minutes - 35.9 minutes elution time). From the peak area ratio of 1,6-bis(ethenylthio)naphthalene and the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8, it was confirmed that the content of the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 was 36%.

[0180] Example 2 Synthesis of Naphthalene Compound Represented by Chemical Formula (I-1) 3.00 g (12.3 mmol) of 1,6-bis(ethenylthio)naphthalene and 12.00 g of toluene were placed in a 50 mL flask, and 0.47 g (2.4 mmol) of 1,6-naphthalenedithiol dissolved in 0.47 g of toluene was added dropwise to the mixture while stirring at 60°C. The mixture was then stirred at 60°C for 3 hours. The mixture was then cooled to room temperature and concentrated under reduced pressure to obtain 3.47 g of a pale yellow liquid.

[0181] The resulting pale yellow liquid １ H-NMR chart (CDCl ３) A signal derived from ethylene chains was observed at 3.06-3.24 ppm. The resulting pale yellow liquid was also analyzed by gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 x 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 x 300 mm, 3.0 μm x 2), detector: PDA (210 nm)). It was confirmed that the pale yellow liquid contained 1,6-bis(ethenylthio)naphthalene as the main component (peak at 37.4 minutes elution time), and further contained a naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 (peak at 25.7 minutes - 35.9 minutes elution time). From the peak area ratio of 1,6-bis(ethenylthio)naphthalene and the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8, it was confirmed that the content of the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 was 43.5%.

[0182] Example 3 Synthesis of Naphthalene Compound Represented by Chemical Formula (I-1) A 50 mL flask was charged with 3.00 g (12.3 mmol) of 1,6-bis(ethenylthio)naphthalene and 12.00 g of toluene, and 0.59 g (3.1 mmol) of 1,6-naphthalenedithiol dissolved in 0.59 g of toluene was added dropwise while stirring at 60°C. The mixture was then stirred at 60°C for 3 hours. The mixture was then cooled to room temperature and concentrated under reduced pressure to obtain 3.56 g of a pale yellow slurry.

[0183] The resulting pale yellow slurry １ H-NMR chart (CDCl ３A signal derived from ethylene chains was observed at 3.06-3.24 ppm of the eluate. The resulting pale yellow slurry was subjected to gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 x 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 x 300 mm, 3.0 μm x 2), detector: PDA (210 nm)). It was confirmed that the pale yellow slurry contained 1,6-bis(ethenylthio)naphthalene as the main component (peak at 37.4 minutes elution time), and further contained a naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 (peak at 25.3 minutes to 35.5 minutes elution time). From the peak area ratio of 1,6-bis(ethenylthio)naphthalene and the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8, it was confirmed that the content of the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 was 49.9%.

[0184] Example 4 Synthesis of Naphthalene Compound Represented by Chemical Formula (I-1) 3.00 g (12.3 mmol) of 1,6-bis(ethenylthio)naphthalene and 12.00 g of toluene were placed in a 50 mL flask, and 0.71 g (3.7 mmol) of 1,6-naphthalenedithiol dissolved in 0.71 g of toluene was added dropwise while stirring at 60°C. The mixture was then stirred at 60°C for 3 hours. After that, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain 3.71 g of a pale yellow slurry.

[0185] The resulting pale yellow slurry １ H-NMR chart (CDCl ３A signal derived from ethylene chains was observed at 3.06-3.24 ppm. The resulting pale yellow slurry was also subjected to gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 x 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 x 300 mm, 3.0 μm x 2), detector: PDA (210 nm)). The pale yellow slurry was confirmed to contain 1,6-bis(ethenylthio)naphthalene as the main component (peak at 37.4 minutes elution time), and also to contain a naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 (peak at 24.0 minutes - 35.4 minutes elution time). From the peak area ratio of 1,6-bis(ethenylthio)naphthalene and the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8, it was confirmed that the content of the naphthalene compound represented by chemical formula (I-1) in which n is 1 to 8 was 59.1%.

[0186] Example 5 Synthesis of Naphthalene Compound Represented by Chemical Formula (I-2) 2.00 g (8.2 mmol) of 1,6-bis(ethenylthio)-naphthalene and 8.00 g of ethyl acetate were placed in a 50 mL flask, and 0.51 g (2.0 mmol) of 4,4'-thiobisbenzenethiol dissolved in 4.61 g of ethyl acetate was added dropwise while stirring at 60°C. The mixture was then stirred at 60°C for 3 hours. After that, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain 2.50 g of an orange liquid.

[0187] The resulting orange liquid １ H-NMR chart (CDCl ３) and a signal derived from ethylene chains was observed at 3.01-3.22 ppm. The resulting orange liquid was subjected to gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 x 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 x 300 mm, 3.0 μm x 2), detector: PDA (210 nm)). It was confirmed that the orange liquid contained 1,6-bis(ethenylthio)naphthalene as the main component (peak at 37.4 minutes elution time), and further contained a naphthalene compound represented by chemical formula (I-2) in which n is 1 to 8 (peak at 23.5 minutes-35.9 minutes elution time). From the peak area ratio of 1,6-bis(ethenylthio)naphthalene and the naphthalene compound represented by chemical formula (I-2) in which n is 1 to 8, it was confirmed that the content of the naphthalene compound represented by chemical formula (I-2) in which n is 1 to 8 was 51.7%.

[0188] [Evaluation Test (Measurement of Refractive Index)] Evaluation tests (measurement of refractive index) were carried out on the products (reaction mixtures) and 1,6-bis(ethenylthio)naphthalene obtained in Examples 1 to 5, and the test results obtained are as shown in Table 3.

[0189]

[0190] From Table 3, it was confirmed that the products obtained in Examples 1 to 5 contain the compound represented by chemical formula (I-1) or the compound represented by chemical formula (I-2), and therefore have higher refractive indices than the conventional naphthalene compound (Comparative Example 1).

[0191] Example 6: 100 parts by weight of the product obtained in Example 2 were mixed with 66.0 parts by weight of 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril and 0.6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to obtain a photosensitive resin composition. This photosensitive resin composition was applied to a glass substrate to a thickness of 100 μm to form a coating film. This coating film was exposed to monochromatic light of 365 nm in air using an ultraviolet irradiation device at an exposure dose of 2,000 mJ / cm. ２This cured film was subjected to an evaluation test (measurement of refractive index), and the test results obtained are shown in Table 4.

[0192] Comparative Example 2: 100 parts by weight of 1,6-bis(ethenylthio)naphthalene were mixed with 93.0 parts by weight of 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril and 0.6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to obtain a photosensitive resin composition. This photosensitive resin composition was applied to a glass substrate to a thickness of 100 μm to form a coating film. This coating film was exposed to monochromatic light of 365 nm in air using an ultraviolet irradiation device at an exposure dose of 2,000 mJ / cm. ２ This cured film was subjected to an evaluation test (measurement of refractive index), and the test results obtained are shown in Table 4.

[0193]

[0194] The naphthalene compound of the present invention is novel and characterized by a high refractive index. Polymerization of a composition containing the naphthalene compound can provide a cured product with a high refractive index. Therefore, the resin composition of the present invention is suitable as a material used in producing coating materials, inks, adhesives, pressure-sensitive adhesives, gas barrier films, color filters, prisms, diffraction gratings, optical mirrors, optical films, optical lenses, etc.

Claims

1. A naphthalene compound represented by chemical formula (I). (In the formula, Y represents a group selected from formulas (1) to (7), and n represents an integer of 1 to 10.) (In the formula, m1 represents an integer of 1 to 3. m2 represents an integer of 1 or 2. m3 is the same and represents an integer of 1 to 3. m4 represents an integer of 1 to 3.) 2. The naphthalene compound according to claim 1, wherein in chemical formula (I), Y is a group selected from (1) to (3).

3. A composition comprising the naphthalene compound of claim 1 and a bis(ethenylthio)naphthalene compound represented by chemical formula (III).

4. A resin composition comprising the naphthalene compound according to claim 1 or the composition according to claim 3.

5. The resin composition according to claim 4, which contains one member selected from the group consisting of a radical polymerization initiator, a cationic polymerization initiator, and a polysiloxane compound.

6. A cured product of the resin composition according to claim 4.

7. A method for synthesizing the naphthalene compound represented by chemical formula (I) according to claim 1, characterized by reacting a dithiol compound represented by chemical formula (II) with a bis(ethenylthio)naphthalene compound represented by chemical formula (III). (In the formula, Y is the same as defined above.)

Images