Fluorene skeleton-containing (meth)acrylate compound, resin composition, and cured product

Abstract

To provide a novel (meth)acryloyl group-containing fluorene compound that yields a cured product with improved elongation compared with traditional fluorene skeleton-containing (meth)acrylate compounds.SOLUTION: Provided is a fluorene skeleton-containing (meth)acrylate compound containing an alkenyl group having a double bond at the terminal thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fluorene skeleton-containing (meth)acrylate compound, a resin composition, and a cured product thereof. [Background technology]

[0002] Polyfunctional (meth)acrylates synthesized from bisphenols are widely used in coating agents, lenses, displays, etc. In recent years, with the increasing functionality of optical materials, these polyfunctional (meth)acrylates are required to have improved properties such as heat resistance and refractive index.

[0003] Among bisphenols, 9,9-bisphenolfluorene compounds are known to have excellent heat resistance and a high refractive index, and polyfunctional (meth)acrylate compounds derived from such compounds are also used.

[0004] For example, Patent Document 1 discloses a lens material that is a composition containing, as a main component, a polyfunctional (meth)acrylate derived from 9,9-bisphenol fluorene represented by the following formula (X). [ka] (In the formula, R A , R B represents hydrogen or a methyl group, and m and n represent integers of 0 to 5.

[0005] Furthermore, Patent Document 2 discloses a polymerizable composition comprising a specific polyfunctional (meth)acrylate having a fluorene skeleton, a hydrolysis-condensation-type organosilicon compound having a polymerizable group, a photoacid generator, and a photoradical initiator, and the polyfunctional (meth)acrylate includes (meth)acrylates of 9,9-bis(mono- to trihydroxyphenyl)fluorenes, alkylene oxides of 9,9-bis(mono- to trihydroxyphenyl)fluorenes (C 2-4 (Meth)acrylates of alkylene oxide adducts, etc. are described.

[0006] While the use of these compounds can improve the heat resistance and refractive index of resins, the introduction of a rigid fluorene skeleton generally results in low elongation and brittle resins, which is a problem. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 3130555 [Patent Document 2] Patent No. 4756977 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and aims to provide a new fluorene skeleton-containing (meth)acrylate compound that has a cured product with a superior elongation percentage compared to conventional fluorene skeleton-containing (meth)acrylate compounds, a resin composition containing the compound, and a cured product obtained from the resin composition. [Means for solving the problem]

[0009] As a result of extensive investigations to achieve the above object, the present inventors have found that a fluorene skeleton-containing (meth)acrylate compound having an alkenyl group with a double bond at the terminal thereof improves the elongation of the cured product compared to when a conventional fluorene skeleton-containing (meth)acrylate compound is used, and have thus completed the present invention.

[0010] That is, the present invention provides the following fluorene skeleton-containing (meth)acrylate compound, resin composition, and cured product. 1. A (meth)acrylate compound having a fluorene skeleton and containing an alkenyl group having a double bond at the terminal. 2. A fluorene skeleton-containing (meth)acrylate compound 1, which is represented by the following formula (1): [ka] (In the formula, n 1 and n 2 are each independently an integer of 1 to 7. R 1 ~R 4 are each independently a hydrogen atom or a methyl group. L 1 and L 2 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 3.L 1 and L 2 and (meth)acrylate compounds (2) containing a fluorene skeleton, wherein both of the above are saturated hydrocarbylene groups in which one or more hydrogen atoms have been substituted with hydroxy groups, or saturated hydrocarbylene groups in which one or more -CH2- have been substituted with -CONH-. 4.n 1 and n 2 and (meth)acrylate compounds having a fluorene skeleton of 2 or 3, wherein both of them are 1. 5.L 1 and L 2 and (meth)acrylate compounds having a fluorene skeleton of any one of 2 to 4, each of which has 1 to 8 carbon atoms. 6. A resin composition comprising the fluorene skeleton-containing (meth)acrylate compound of any one of 1 to 5 and a polymerization initiator. A cured product obtained from the resin composition of 7.6. [Effects of the Invention]

[0011] The fluorene skeleton-containing (meth)acrylate compound of the present invention can provide a coating having improved elongation compared to the case where a conventionally used fluorene skeleton-containing (meth)acrylate compound is used. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Fluorene skeleton-containing (meth)acrylate compounds] The fluorene skeleton-containing (meth)acrylate compound of the present invention contains an alkenyl group having a terminal double bond.

[0013] Such a compound is preferably one represented by the following formula (1). [ka]

[0014] In formula (1), n 1 and n 2 are each independently an integer of 1 to 7, more preferably an integer of 1 to 3, and even more preferably 1.

[0015] In formula (1), R 1 ~R 4 are each independently a hydrogen atom or a methyl group, but R 1 and R 2 is preferably a hydrogen atom.

[0016] In formula (1), L 1 and L 2 are each independently a saturated hydrocarbylene group having 1 to 15 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. The -CH2- groups of the saturated hydrocarbylene group may be located at its terminal.

[0017] The saturated hydrocarbylene group may be linear, branched, or cyclic, and specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,1 alkanediyl groups having 1 to 15 carbon atoms, such as 0-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, and pentadecane-1,15-diyl group; and cyclic saturated hydrocarbylene groups having 3 to 15 carbon atoms, such as cyclopentanediyl group, cyclohexanediyl group, norbornanediyl group, and adamantanediyl group.

[0018] L 1 and L 2 and preferably each have 1 to 8 carbon atoms, and more preferably have one or more hydrogen atoms substituted with a hydroxy group, or one or more -CH2- groups substituted with -CONH- groups.

[0019] [Method for producing a fluorene skeleton-containing (meth)acrylate compound] The method for producing the fluorene skeleton-containing (meth)acrylate compound of the present invention is not particularly limited, but for example, the compound can be synthesized by reacting a 9,9-bisphenolfluorene compound having an alkenyl group having a double bond at its terminal, represented by the following formula (2), with a compound represented by the following formula (3). [ka] (In the formula, n 1 , n 2 , R 3 and R 4 is the same as above.)

[0020] In formula (3), R 5 is a hydrogen atom or a methyl group.

[0021] In formula (3), L3 is a saturated hydrocarbylene group having 1 to 14 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 3 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, but preferably has 1 to 7 carbon atoms.

[0022] Specific examples of the compound represented by formula (3) include, but are not limited to, 2-acryloyloxyethyl isocyanate (Karenz AOI (registered trademark) manufactured by Showa Denko K.K.), 2-methacryloyloxyethyl isocyanate (Karenz MOI (registered trademark) manufactured by Showa Denko K.K.), and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz MOI-EG (registered trademark) manufactured by Showa Denko K.K.).

[0023] The reaction conditions are not particularly limited, but typically involve mixing a compound represented by formula (2) and a compound represented by formula (3) in a solvent and heating the mixture. As the solvent, aprotic polar solvents are preferred from the viewpoint of promoting the reaction while suppressing side reactions, and particularly preferred are ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate. The reaction temperature is preferably 35 to 130°C, particularly 45 to 100°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time, which varies depending on the type and amount of the reaction substrate, is preferably approximately 0.5 to 50 hours, particularly 0.5 to 24 hours.

[0024] In the reaction, the raw material compounds are preferably mixed so that the molar ratio of the compound represented by formula (3) to the compound represented by formula (2) is 1.80 to 2.20, more preferably 1.95 to 2.10. Only one type of compound represented by formula (2) and one type of compound represented by formula (3) may be used, or two or more types of compounds may be used in combination.

[0025] In the reaction, a catalyst may be optionally used. Examples of the catalyst include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; pyridines such as pyridine, N,N-dimethyl-4-aminopyridine, and 2,6-lutidine; tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, and dimethyltin. organic lead compounds such as lead octoate and lead naphthenate; organic nickel compounds such as nickel naphthenate; organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octenate; organic bismuth compounds such as bismuth octylate and bismuth neodecanoate; and potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

[0026] The amount of the catalyst used is usually a catalytic amount, and is preferably an amount of 0.1 to 20 mol % relative to the compound represented by formula (2). The catalyst may be used alone or in combination of two or more.

[0027] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the compound represented by formula (3).

[0028] After the reaction is complete, optionally, a solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, thereby obtaining the compound represented by formula (1). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0029] Another method for producing the compound represented by formula (1) includes the reaction of a compound represented by formula (2) with a compound represented by the following formula (4). [ka]

[0030] In formula (4), R 6 is a hydrogen atom or a methyl group.

[0031] In formula (4), L 4 is a divalent saturated hydrocarbylene group having 1 to 13 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 3 The saturated hydrocarbylene group represented by the following formula may be linear, branched or cyclic, but preferably has 1 to 6 carbon atoms.

[0032] The reaction conditions are not particularly limited, but typically involve mixing a compound represented by formula (2) and a compound represented by formula (4) in a solvent and heating the mixture. As the solvent, aprotic polar solvents are preferred from the viewpoint of promoting the reaction while suppressing side reactions, and ketones such as cyclopentanone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate are particularly preferred. The reaction temperature is preferably 35 to 130°C, particularly 45 to 100°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time, which varies depending on the type and amount of the reaction substrate, is preferably approximately 0.5 to 50 hours, particularly 0.5 to 24 hours.

[0033] In the reaction, the raw material compounds are preferably mixed so that the molar ratio of the compound represented by formula (4) to the compound represented by formula (2) is 1.60 to 3.00, more preferably 1.90 to 2.00. Only one type of compound represented by formula (2) and one type of compound represented by formula (4) may be used, or two or more types of compounds may be used in combination.

[0034] In the reaction, a catalyst may be optionally used. Examples of the catalyst include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; imidazoles such as imidazole and 2-ethyl-4-methylimidazole; potassium salts such as potassium hydroxide, potassium carbonate, potassium acetate, and potassium octoate; and sodium salts such as sodium hydroxide, sodium carbonate, sodium acetate, and sodium octoate.

[0035] The amount of the catalyst used is usually a catalytic amount, and is preferably an amount of 0.1 to 20 mol % relative to the compound represented by formula (2). The catalyst may be used alone or in combination of two or more.

[0036] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor that can be used include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the compound represented by formula (4).

[0037] After the reaction is complete, optionally, a solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, thereby obtaining the compound represented by formula (1). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0038] Another method for producing the compound represented by formula (1) is to react the compound represented by formula (5) with acrylic acid or methacrylic acid. [ka] (In the formula, n 1 , n 2 , R 1 and R 2 is the same as above.)

[0039] In formula (5), L 5 and L 6 are each independently a saturated hydrocarbylene group having 1 to 13 carbon atoms, in which some of the -CH2- groups may be substituted with -O-, -S-, -SO2-, -CO- or -CONH-, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups. 5 and L 6The saturated hydrocarbylene group represented by the following formula may be linear, branched or cyclic, but preferably has 1 to 6 carbon atoms.

[0040] The reaction conditions are not particularly limited, but typically involve mixing the compound represented by formula (5) and acrylic acid or methacrylic acid in a solvent and heating the mixture. From the viewpoint of accelerating the reaction, a polar solvent is preferably used as the solvent, and an alcohol solvent such as propylene glycol monomethyl ether is particularly preferred. The reaction temperature is preferably 35 to 130°C, and more preferably 60 to 110°C, from the viewpoint of preventing side reactions and enabling the reaction to be completed in a short time. The reaction time varies depending on the type and amount of the reaction substrate, but is preferably approximately 0.5 to 50 hours, and more preferably 0.5 to 24 hours.

[0041] In the reaction, the raw material compounds are preferably mixed so that the molar ratio of acrylic acid or methacrylic acid to the compound represented by formula (5) is 2.00 to 10.00, more preferably 3.00 to 8.00. As the compound represented by formula (5), only one type of compound may be used, or two or more types of compounds may be used in combination. Furthermore, either acrylic acid or methacrylic acid may be used alone, or both may be used in combination.

[0042] In the reaction, a catalyst may be optionally used. Examples of the catalyst include amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine; phosphines such as triphenylphosphine and tri(o-tolyl)phosphine; quaternary ammonium salts such as tetrabutylammonium chloride, benzyltriethylammonium chloride, and tetraethylhydroxylammonium; and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

[0043] The amount of the catalyst used is usually a catalytic amount, and is preferably an amount of 0.1 to 20 mol % relative to the compound represented by formula (5). The catalyst may be used alone or in combination of two or more.

[0044] In the reaction, a polymerization inhibitor may be optionally used. Examples of the polymerization inhibitor that can be used include various phenols, hydroquinones, benzoquinones, catechols, hydroxyamines, and nitroso compounds. The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the acrylic acid or methacrylic acid.

[0045] After the reaction is complete, optionally, a solvent may be added, the mixture may be washed with water, and the organic layer may then be heated under reduced pressure to remove the solvent, thereby obtaining the compound represented by formula (1). When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal hydrogencarbonate such as sodium carbonate, sodium hydrogencarbonate or potassium carbonate may be used.

[0046] [Resin composition] The resin composition of the present invention contains (A) the compound represented by the above formula (1) and (B) a polymerization initiator.

[0047] [(B) Polymerization initiator] As the polymerization initiator, known ones can be used, and examples thereof include thermal radical generators and photoradical generators.

[0048] Examples of the thermal radical generator include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxy peroxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy) Di)butane, t-butyl peroxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1, Examples of suitable peroxides include organic peroxides such as 3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and benzoyl peroxide; and azo compounds such as azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, and 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide].

[0049] Examples of the photoradical generator include alkylphenone-type initiators such as 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one; acylphosphine oxide-type initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Irgacure Oxe01 (BASF Japan Ltd.), Irgacure Oxe02 (BASF Japan Ltd.), Irgacure Oxe03 (BASF Japan Ltd.), and Irgacure Examples of such initiators include oxime ester initiators such as Oxe04 (BASF Japan Ltd.), N-1919T (ADEKA Corporation), NCI-730 (ADEKA Corporation), NCI-831E (ADEKA Corporation), and NCI-930 (ADEKA Corporation).

[0050] In the resin composition of the present invention, the content of component (B) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). When the content of component (B) is within the above range, sufficient curability is easily obtained, and deterioration of the physical properties of the cured film due to the polymerization initiator can be prevented. The polymerization initiator for component (B) may be used alone, or two or more types may be used in combination.

[0051] [(C) Radical polymerizable compound] The resin composition of the present invention may further comprise, as component (C), a radically polymerizable compound different from component (A). The radically polymerizable compound of component (C) is capable of undergoing a radical polymerization reaction with the (meth)acryloyl group of component (A), thereby further increasing the strength of the resin film after curing. Specific examples of the radically polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth)acrylic acid ester compounds.

[0052] The radical polymerizable compound of component (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tri(meth)acrylate, tetra ... Examples of the acrylate copolymer include 2-(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0053] The content of component (C) in the resin composition of the present invention is 0 to 100 parts by mass, preferably 1.0 to 80 parts by mass, and more preferably 1.0 to 50 parts by mass, per 100 parts by mass of component (A). If the content of component (C) is 0.5 parts by mass or more, sufficient curability is obtained, and if it is 100 parts by mass or less, the proportion of component (A) in the composition does not decrease, allowing the cured product to fully exhibit the effects of the present invention. The radically polymerizable compound of component (C) may be used alone or in combination of two or more.

[0054] [(D) Solvent] The resin composition of the present invention may contain a solvent as component (D) to improve its coatability. The solvent for component (D) is not particularly limited as long as it can dissolve the above-mentioned components (A) to (C), the below-described component (E), and various other additives.

[0055] The solvent is preferably an organic solvent, and specific examples thereof include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone.

[0056] As the (D) solvent, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof are particularly preferred, as they have excellent solubility for the polymerization initiator.

[0057] In the resin composition of the present invention, the content of component (D) is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of components (A) and (C) combined, from the viewpoints of compatibility and viscosity of the resin composition. The solvent for component (D) may be used alone or in combination of two or more.

[0058] [(E) Antioxidant] The resin composition of the present invention may contain an antioxidant as an additive. By containing an antioxidant, heat resistance can be improved. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds.

[0059] The hindered phenol compound is not particularly limited, but the following are preferred: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester (trade name: IRGANOX 1330), 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) (trade name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name: Seenox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-Tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adekastab AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: Adekastab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (trade name: IRGANOX 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzyl ethyl phosphonate) calcium / polyethylene wax mixture (50:50) (trade name: IRGANOX 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine (trade name: Sumilizer GP), etc.

[0060] The hindered amine compound is not particularly limited, but the following compounds are preferred. For example, p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade names: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacloryloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-Triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 770), bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: TINUVIN 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol Examples of suitable esters include a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylenecarboxylate (trade name: Adekastab LA-82), and (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylenecarboxylate (trade name: Adekastab LA-87).

[0061] The content of component (E) in the resin composition of the present invention is not particularly limited as long as it does not impair the effects of the present invention, but when it is contained, it is preferably 0.01 to 1 mass% in the resin composition of the present invention. The antioxidant of component (E) may be used alone or in combination of two or more.

[0062] [Other additives] The resin composition of the present invention may contain other additives in addition to the above-mentioned components. Examples of the additives include surfactants that are commonly used to improve coatability.

[0063] The surfactant is preferably a nonionic surfactant, and examples thereof include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. Commercially available surfactants can be used, such as Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031, and DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Of these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant in the resin composition of the present invention is not particularly limited as long as it does not impair the effects of the present invention, but when it is contained, it is preferably 0.01 to 1 mass % in the resin composition of the present invention.

[0064] A silane coupling agent can also be used as an additive. By including a silane coupling agent, the adhesion of the resin composition to the adherend can be further improved. Examples of the silane coupling agent include epoxy silane coupling agents and aromatic-containing amino silane coupling agents. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but when it is included, it is preferably 0.01 to 5 mass% in the resin composition of the present invention.

[0065] The method for preparing the resin composition of the present invention is not particularly limited, but examples thereof include a method in which the components are stirred and mixed, and then, if necessary, filtered with a filter or the like to remove solids.

[0066] [Cured product] The cured product of the present invention is obtained from the resin composition. When the resin composition contains only a thermal radical generator as a polymerization initiator, (i) forming a resin film on a substrate using the resin composition; and (ii) a step of heating the resin film A cured product can be obtained by a method comprising the steps of:

[0067] Step (i) is a step of forming a resin film on a substrate using the resin composition, such as a silicon wafer, a glass wafer, a quartz wafer, a plastic circuit board, or a ceramic circuit board.

[0068] The resin film can be formed by a known method. For example, it can be formed by applying the resin composition to a substrate by a method such as dipping, spin coating, or roll coating. The amount of coating can be appropriately selected depending on the purpose, but an amount that results in a film thickness of 0.1 to 100 μm is preferred.

[0069] Here, in order to efficiently carry out the subsequent curing reaction, the solvent may be evaporated in advance by preheating as necessary. Preheating can be carried out, for example, at 40 to 160°C for about 1 minute to 1 hour.

[0070] Step (ii) is a step of heating and curing the resin film. The heating conditions are appropriately selected depending on the types of fluorene skeleton-containing (meth)acrylate compound, thermal radical generator, and radical polymerizable compound used, but the heating is preferably performed at 50 to 250°C for about 10 minutes to 6 hours.

[0071] Furthermore, when a photoradical generator is contained as a polymerization initiator, the resin composition of the present invention has photosensitivity. (i) forming a resin film on a substrate using the resin composition; (ii) exposing the resin film to light; and (iii) developing the exposed resin film using a developer A cured product having a fine pattern can be produced by the method comprising the steps of:

[0072] Step (i) is the same as described above.

[0073] Next, in step (ii), the resin film is exposed to light. At this time, it is preferable to expose to light having a wavelength of 240 to 500 nm. Examples of the light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line and i-line, and far ultraviolet light (248 nm). The exposure dose is 10 to 5000 mJ / cm. 2 is preferred.

[0074] The exposure may be performed through a photomask. The photomask may be, for example, hollowed out to have a desired pattern. The material of the photomask is preferably one that blocks light having a wavelength of 240 to 500 nm, and suitable materials include, but are not limited to, chromium.

[0075] Step (iii) is a step of developing the resin film after exposure using a developer. The developer is preferably an organic solvent-based developer used as a solvent, such as isopropyl alcohol, propylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate. Development using the organic solvent-based developer dissolves and removes the unexposed areas to obtain a negative pattern. Development can be performed by a conventional method, for example, by immersing the substrate on which the pattern has been formed in the developer. Thereafter, washing, rinsing, drying, or the like is performed as necessary to obtain a film having the desired pattern.

[0076] The pattern formation method is as described above. However, when it is not necessary to form a pattern, for example, when it is desired to simply form a uniform film using a resin composition containing a photoradical generator, in step (ii) of the pattern formation method, the film can be formed by exposing the resin composition to light of an appropriate wavelength without using the photomask.

[0077] The cured film produced by the above method is a cured product with excellent heat resistance and refractive index. The cured product preferably has an elongation of 70% or more, more preferably 80% or more, and even more preferably 90% or more. [Example]

[0078] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0079] [1] Synthesis of fluorene skeleton-containing (meth)acrylate compounds The compounds used in the synthesis are shown below. [ka]

[0080] [ka]

[0081] [Example 1-1] Synthesis of Compound 1 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser, 430.6 g (1.00 mol) of the compound represented by formula (S-1a) was dissolved in 1800 g of propylene glycol monomethyl ether acetate. 282.2 g (2.00 mol) of the compound represented by formula (S-2a) and 12.2 g (0.10 mol) of N,N-dimethyl-4-aminopyridine were then added, heated to 60°C, and stirred for 8 hours. The reaction solution was allowed to cool to room temperature and washed with pure water. The organic layer was then heated and concentrated under reduced pressure to obtain compound 1. Compound 1 was characterized by the ultraviolet-visible absorption spectrum and 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the compound was the compound represented by the following formula (A1). 1 H-NMR (CDCl3): δ= 3.22 (4H, d, J=6.3Hz), 3.51(4H, t, J=7.1Hz), 4.39 (4H, t, J=7.1Hz), 4.75-4.90 (4H, m), 5.76 (2H, ddt, J=17.1, 10.6, 6.3Hz), 6.02 (2H, dd, J=10.9, 1.5Hz), 6.33 (2H, dd, J=17.0, 1.5Hz), 6.51 (2H, dd, J=1.1, 0.5Hz), 6.65 (2H, br), 6.86 (2H, dd, J=17.0, 10.9Hz), 7.04 (2H, dd, J=8.7, 1.1Hz), 7.24 (2H, dd, J=8.7, 0.5Hz), 7.31-7.45 (4H, m), 7.64 (2H, dd, J=8.1, 1.4), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0082] [Example 1-2] Synthesis of Compound 2 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, 486.7 g (1.00 mol) of the compound represented by formula (S-1b) was dissolved in 1800 g of propylene glycol monomethyl ether acetate. 312.4 g (2.00 mol) of the compound represented by formula (S-2b) and 20.2 g (0.20 mol) of triethylamine were then added, heated to 80°C, and stirred for 10 hours. The reaction solution was allowed to cool to room temperature, dissolved in aqueous sodium bicarbonate, washed with pure water, and the organic layer was heated and concentrated under reduced pressure to obtain compound 2. Compound 2 was characterized by its UV-visible absorption spectrum and 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the compound was the compound represented by formula (A2). 1 H-NMR (CDCl3): δ= 1.47-1.70 (8H, m), 1.85-2.04 (8H, m), 2.58-2.69 (4H, m), 2.97 (2H, br), 3.70-3.81 (2H, m), 3.96-4.08 (4H, m), 4.20-4.31 (4H, m), 4.73-4.88 (4H, m), 5.64 (2H, ddt, J=16.9, 10.4, 7.4Hz), 6.02 (2H, dd, J=10.9, 1.5Hz), 6.37 (2H, dd, J=17.0, 1.5Hz), 6.75-6.95 (6H, m), 7.06 (2H, dd, J=8.4, 1.3Hz), 7.31-7.45 (4H, m), 7.64 (2H, dd, J=8.1, 1.4Hz), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0083] [Examples 1-3] Synthesis of Compound 3 In a 10 L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser, 542.7 g (1.00 mol) of the compound represented by formula (S-1c) was dissolved in 1800 g of propylene glycol monomethyl ether. 516.4 g (6.00 mol) of methacrylic acid and 22.8 g (0.10 mol) of benzyltriethylammonium chloride were then added, followed by heating to 100°C and stirring for 12 hours. The reaction solution was allowed to cool to room temperature, and 1000 g of methyl isobutyl ketone was added. The sodium bicarbonate aqueous solution was allowed to cool, washed with pure water, and the organic layer was heated and concentrated under reduced pressure to obtain compound 3. Compound 3 was characterized by its UV-visible absorption spectrum and 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the compound was the compound represented by formula (A3). 1H-NMR (CDCl3): δ= 1.86 (6H, s), 2.78 (2H, br), 3.15-3.26 (4H, m), 3.93-4.04 (4H, m), 4.10-4.12 (2H, m), 4.47-4.59 (4H, m), 4.76-4.91 (4H, m), 5.56 (2H, d, J=3.9Hz), 5.75 (2H, ddt, J=17.1, 10.6, 6.3Hz), 6.05 (2H, d, J=3.9Hz), 6.76-6.88 (4H, m), 7.06 (2H, dd, J=8.4, 1.3Hz), 7.31-7.45 (4H, m), 7.64 (2H, dd, J=8.1, 1.4Hz), 7.85 (2H, dd, J=8.5, 1.5Hz). [ka]

[0084] [Comparative Example 1-1] According to the method described in Synthesis Example 1 of Japanese Patent No. 3130555, 9,9-bis(methacryloxyphenyl)-fluorene, which is comparative compound 1 represented by the following formula (B1), was synthesized. [ka]

[0085] [Comparative Example 1-2] According to the method described in Synthesis Example 2 of Japanese Patent No. 3130555, 9,9-bis(methacryloxydiethoxyphenyl)-fluorene, which is comparative compound 2 represented by the following formula (B2), was synthesized. [ka]

[0086] [2] Preparation and evaluation of resin compositions [Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-4] The components were mixed and dissolved to a uniform consistency so as to obtain the composition shown in Table 1 below, and then microfiltration was carried out using a 0.2 μm Teflon (registered trademark) filter to prepare a resin composition.

[0087] [Table 1]

[0088] [Elongation measurement] Each resin composition was applied to a polyethylene terephthalate film (38 μm) as a support substrate using a Baker-type applicator SA-201 manufactured by Tester Sangyo Co., Ltd., and heated at 120°C for 3 minutes to remove the solvent, producing a coating (20 μm thick). Each resulting coating was irradiated with 2000 mJ of light at a wavelength of 365 nm to prepare a cured product. JIS No. 5 dumbbell-shaped test specimens were punched out from the resulting cured product, and the support substrate film was peeled off. A tensile test was performed using a Strograph V10-D manufactured by Toyo Seiki Seisaku-sho, Ltd. (extension speed: 50 mm / min). Five test specimens for each composition were measured, and the elongation was calculated from the break distance and the initial distance, and the average value was calculated.

[0089] [Table 2]

[0090] The above results demonstrate that the fluorene skeleton-containing (meth)acrylate compound of the present invention can improve the elongation of the cured product compared to conventionally used fluorene skeleton-containing (meth)acrylate compounds.

Claims

1. A (meth)acrylate compound having a fluorene skeleton and containing an alkenyl group having a double bond at its terminal, represented by the following formula (1): 【Chemistry 1】 (wherein n 1 and n 2 each independently represent an integer of 1 to 7. R 1 to R 4 are each independently a hydrogen atom or a methyl group. L 1 and L 2 each independently represent a saturated hydrocarbylene group having 1 to 15 carbon atoms, in which some of the —CH 2 — groups may be substituted with —O—, —S—, —SO 2 —, —CO— or —CONH—, and some or all of the hydrogen atoms of the saturated hydrocarbylene group may be substituted with hydroxy groups.

2. L 1 and L 2 and each of which is a saturated hydrocarbylene group in which one or more hydrogen atoms have been replaced by a hydroxy group, or one or more —CH 2 2. The (meth)acrylate compound having a fluorene skeleton according to claim 1, wherein - is a saturated hydrocarbylene group substituted with -CONH-.

3. n 1 and n 2 and n is 1. The (meth)acrylate compound having a fluorene skeleton according to claim 1, wherein both of n and n are 1.

4. L 1 and L 2 2. The (meth)acrylate compound having a fluorene skeleton according to claim 1, wherein each of the carbon atoms of is 1 to 8.

5. A resin composition comprising the fluorene skeleton-containing (meth)acrylate compound according to any one of claims 1 to 4 and a polymerization initiator.

6. A cured product obtained from the resin composition according to claim 5.

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