Epoxy amine adduct, curing catalyst, resin composition, encapsulant, adhesive, and cured product

Abstract

[Problem] The purpose of the present invention is to provide an epoxy amine adduct which has favorable properties, a curing catalyst, a resin composition, a sealing material, an adhesive and a cured article. [Solution] The present invention prepares an epoxy amine adduct which, when measured using differential scanning calorimetry (DSC), exhibits a value (melting start temperature at a temperature increase rate of 50° / min) / (melting start temperature at a temperature increase rate of 10° / min) of 1.00-1.10, inclusive, and also prepares an epoxy resin curing catalyst which contains said epoxy amine adduct, a resin composition which contains said curing catalyst, a sealing material or adhesive which contains said resin composition, and a cured article obtained by curing said resin composition.

Description

Technical Field

[0001] The present invention relates to an epoxyamine adduct, a curing catalyst, a resin composition, a sealing material, an adhesive, and a cured product.

Background Art

[0002] One-component epoxy resin adhesives contain a main agent and a curing catalyst, and the curing catalyst is considered to be the material that most affects the pot life and curing conditions of the adhesive. Currently, a variety of commercially available curing catalysts are used in one-component epoxy resin adhesives, but types in which functional groups such as amines are modified on thermosetting resins or thermoplastic resins (Japanese Patent Laid-Open No. 59-053526; Japanese Patent Laid-Open No. 3-177418) and types in which an amine-based curing catalyst is covered with a polymer shell are mainstream (Japanese Patent Laid-Open No. 2000-080146).

Summary of the Invention

Problems to be Solved by the Invention

[0003] An object of the present invention is to provide an epoxyamine adduct, a curing catalyst, a resin composition, a sealing material, an adhesive, and a cured product having good characteristics.

Means for Solving the Problems

[0004] One embodiment of the present invention is an epoxyamine adduct in which, in differential scanning calorimetry (DSC), the value of (melting start temperature at a heating rate of 50 ° C. / min) / (melting start temperature at a heating rate of 10 ° C. / min) is 1.00 or more and 1.10 or less. The value of (melting start temperature at a heating rate of 50 ° C. / min) / (melting start temperature at a heating rate of 10 ° C. / min) may be 1.01 or more and 1.05 or less. In differential scanning calorimetry (DSC) at a heating rate of 10 ° C. / min, the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) in melting may be 0.01 or more and 0.10 or less. The absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) may be 0.029 or more and 0.042 or less. The compound adducted to the amine may have a biphenyl skeleton or a naphthyl skeleton and may have one epoxy group.

[0005] Another embodiment of the present invention is a curing catalyst for an epoxy resin containing any of the above epoxyamine adducts.

[0006] A further embodiment of the present invention is a resin composition containing the above curing catalyst.

[0007] A further embodiment of the present invention is a sealing material or an adhesive containing the above resin composition.

[0008] The cured product of the above resin composition is also one embodiment of the present invention.

[0009] A further embodiment of the present invention is a method for producing any of the above epoxyamine adducts, which includes a step of adducting a compound having a biphenyl skeleton or a naphthyl skeleton and having one epoxy group to an amine.

[0010] ==Cross-reference to related documents== This application claims priority based on Japanese Patent Application No. 2020-64473 filed on March 31, 2020, and the entire disclosure of the basic application is incorporated herein by reference.

Brief description of the drawings

[0011]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0012] The object, features, advantages, and ideas of the present invention are clear to those skilled in the art from the description in this specification, and those skilled in the art can easily reproduce the present invention from the description in this specification. The embodiments and specific examples of the invention described below show preferred embodiments of the present invention and are shown for illustration or explanation, and do not limit the present invention thereto. It is clear to those skilled in the art that various modifications and improvements can be made based on the description in this specification within the intention and scope of the present invention disclosed in this specification.

[0013] ==Epoxyamine Adduct== The epoxyamine adduct according to this embodiment has a value of (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) of 1.00 or more and 1.10 or less in differential scanning calorimetry (DSC).

[0014] An epoxyamine adduct showing such characteristics is useful as a curing catalyst for thermosetting resins such as epoxy resins. Hereinafter, the curing catalyst and resin composition using the epoxyamine adduct according to the present invention will be described.

[0015] ==Curing Catalyst== <Structure of Epoxyamine Adduct A> The curing catalyst of the epoxy resin according to this embodiment contains an epoxyamine adduct having the following structural formulas (I) to (IV). In this specification, the curing catalyst means a catalyst that has the function of promoting the initiation and / or progress of polymerization when the main agent self-polymerizes or when the main agent and the curing agent polymerize.

[0016] [Chemical formula] (In the formula, R 1 is a group selected from hydrogen, phenyl, and C1-C17 alkyl, and R 2 , R 3 are each independently a group selected from hydrogen and C1-C6 alkyl.) R 1 may be a group selected from phenyl and C1-C12 alkyl. The alkyl groups of R 1 , R 2 , R 3 may have a linear structure, a branched structure, or a cyclic structure.

[0017] [Chemical formula] (In the formula, R 4 , R 5 are groups selected from hydrogen, phenyl group, and C1-C6 linear, branched, cyclic alkyl groups, aralkyl groups, alkenyl groups, and aryl groups.)

[0018] [Chemical formula] (In the formula, n and m are each 1-4, and the sum of n and m is 3-5, A is CH2, O, NR 6 , and R 6 is a group selected from hydrogen, phenyl group, and C1-C6 linear, branched, cyclic alkyl groups, aralkyl groups, and alkenyl groups.)

[0019] [Chemical formula] (wherein, R 7 is a group selected from hydrogen, phenyl and C1-C17 alkyl, and R 8 , R 9 are each independently a group selected from hydrogen and C1-C6 alkyl.) R 7 may be a group selected from phenyl and C1-C12 alkyl. R 7 , R 8 , R 9 The alkyl groups of may be linear, branched or cyclic.

[0020] (I)-(III) epoxyamine adducts are compounds obtained by reacting a biphenyl compound having one epoxy group with an amine, and (IV) epoxyamine adduct is a compound obtained by reacting a naphthyl compound having one epoxy group with an amine.

[0021] The biphenyl compound and naphthyl compound having one epoxy group may optionally have other substituents, for example, a chain alkyl group (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, etc.), a cycloalkyl group (e.g., cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.), an allyl group, an aryl group (e.g., phenyl group, benzyl group, etc.), an acyl group, an acyloxy group, an alkoxy group, a halogen group, a halogenated alkyl group, a sulfone group, a nitro group, a carboxyl group, etc. The one epoxy group substituting on biphenyl and naphthyl may be substituted at any position.

[0022] The structure of the epoxy preferably has a biphenyl skeleton or a naphthyl skeleton, thereby increasing the pot life. Although the principle of this effect is not limited to the following theory, when the structure of the epoxy in the epoxyamine adduct contains a biphenyl skeleton or a naphthyl skeleton, the solubility of the epoxyamine adduct in the epoxy resin (main component) at room temperature decreases, so it is considered that the pot life becomes longer. Here, as the number of aromatic rings directly or bonded through a carbon-carbon single bond in the epoxy structure in the epoxyamine adduct increases (for example, anthracene skeleton), the solubility in the epoxy resin decreases even at high temperatures, and the solubility in the epoxy resin also decreases during heating, which is not preferable.

[0023] In addition, when the epoxy structure in the epoxyamine adduct is a phenyl skeleton, the pot life becomes short. This is considered to be because the intermolecular interaction of the resulting adduct is low, so the solubility of the curing catalyst in the epoxy resin at room temperature increases.

[0024] Also, in terms of pot life, the number of epoxy groups in the epoxy resin to which the amine adds is preferably one. It is considered that as the number of epoxy groups in the epoxy resin to which the amine adds increases, the pot life tends to deteriorate because the number of added amino groups increases.

[0025] The amines to be adducted include imidazole compounds, primary amine compounds, or secondary amine compounds. Among the imidazole compounds, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole are preferred. From the perspective of achieving both curability and pot life, 2-methylimidazole and 2-undecylimidazole are more preferred. As commercially available products, examples of the imidazole compounds to be adducted include 2MZ-H, C11Z, C17Z, 2PZ, and 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd. When adducted with 2-methylimidazole, for one epoxy group substituted on biphenyl, from the perspective of melting point, the ortho position or meta position is preferred, and the ortho position is more preferred. At the ortho position, the balance between the diffusion of the curing catalyst and the curing reaction at 100 °C or higher is the best. One epoxy group substituted on naphthyl may be at the α-position or β-position, but the α-position is preferred.

[0026] The primary amine compound or secondary amine compound is not particularly limited, and examples thereof include aliphatic amines, alicyclic amines, aromatic amines, etc.

[0027] The aliphatic amine is not particularly limited, and examples thereof include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine.

[0028] The alicyclic amine is not particularly limited, and examples thereof include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, isophoronediamine, pyrrolidine, piperidine, hexamethyleneimine, N-methylpiperazine, N-phenylpiperazine, morpholine, etc.

[0029] The aromatic amine is not particularly limited, and examples thereof include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.

[0030] <Method for producing epoxyamine adduct> (I) to (III) epoxyamine adducts can be produced by reacting a methylimidazole derivative having an imidazole ring with the same modification as the above compound with 2-{[([1,1’-biphenyl]-2-yl)oxy]methyl}oxirane, 2-{[([1,1’-biphenyl]-3-yl)oxy]methyl}oxirane, or 2-{[([1,1’-biphenyl]-4-yl)oxy]methyl}oxirane. However, the production method is not limited to this, and it can be produced using methods known to those skilled in the art.

[0031] (IV) epoxyamine adduct can be produced by reacting a methylimidazole derivative having an imidazole ring with the same modification as the above compound with 2-(naphthalen-1-yloxymethyl)oxirane or 2-(naphthalen-2-yloxymethyl)oxirane. However, the production method is not limited to this, and it can be produced using methods known to those skilled in the art.

[0032] The solvent used in the synthesis reaction of the epoxyamine adduct is not particularly limited. For example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirits, and naphtha; chain ethers such as dimethyl ether, diethyl ether, and ethyl methyl ether; cyclic ethers such as tetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile, propionitrile, and butyronitrile; amides such as acetamide, formamide, N,N-dimethylacetamide, and N,N-dimethylformamide; sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and isophorone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water, etc. These solvents may be used alone or in combination of two or more.

[0033] <Characteristics of the epoxyamine adduct> Since these epoxyamine adducts do not have a BPA (bisphenol A) skeleton, they do not generate BPA, which has been pointed out as a risk to the health of organisms from the cured product, and have high safety. For example, when the epoxyamine adduct disclosed in this specification is used as a curing catalyst for bisphenol A type epoxy resin, the generation of BPA from the cured product can be significantly suppressed as compared with the case of using a conventionally known bisphenol A type epoxyamine adduct. This is considered to be because BPA is generated only from the ends of the polymerized bisphenol A type epoxy resin due to the structure of the polymer.

[0034] Also, as shown in the examples, when used as a curing catalyst for an epoxy resin, it has a long pot life and exhibits sufficient curability. Although the principle of these effects is not restricted to the following theory, it is considered that the pot life becomes long because the affinity between the biphenyl skeleton or naphthyl skeleton contained in the curing catalyst and the epoxy resin is low at room temperature. Further, at 100 °C or higher, the affinity between the biphenyl skeleton or naphthyl skeleton and the epoxy resin increases, so that the diffusion of the curing catalyst and the curing reaction proceed in a well-balanced manner. As a result, the residual amount of the unreacted curing catalyst decreases, and a uniform coating film can be formed by curing.

[0035] The melting points of these epoxyamine adducts can be determined, for example, by the following procedure using a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH). First, 5 mg of each resin composition is weighed into an aluminum pan, sealed with an aluminum lid, and then a hole is made in the center of the lid with a needle to prepare a measurement sample. Next, the heat flow (mW / mg) is measured while heating this measurement sample from 25 °C to 250 °C at a heating rate of 10 °C / min under a nitrogen atmosphere (100 mL / min). The temperature at which the peak top is obtained on the graph is calculated by analysis software (NETZSCH Proteus-Thermal Analysis version 6.1.0B), and this temperature is referred to as the melting peak temperature in this specification.

[0036] Also, when calculating the melting peak temperature as described above, the heat flow (i.e., the maximum heat flow) at the peak temperature and the area of the peak (i.e., the heat of fusion) are analyzed by the analysis software of the apparatus. Then, the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is calculated. Next, in the range of 25 to 250 °C, the heat flow (mW / mg) is measured under the conditions of a heating rate of 10 °C / min and a heating rate of 50 °C / min, and the melting start temperature (°C) under each condition is analyzed, and (melting start temperature at a heating rate of 50 °C / min) / (melting start temperature at a heating rate of 10 °C / min) is calculated as the heating rate dependence.

[0037] The larger the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]), the less likely it is for the curing catalyst to dissolve in the resin in an unintended temperature range, so it can be expected that the pot life will be longer. Also, the smaller the temperature increase rate dependency, the more instantaneously the curing catalyst dissolves in the resin in the intended temperature range, so short-time curability can be expected while maintaining a sufficient pot life.

[0038] The temperature increase rate dependency of these epoxyamine adducts is preferably such that (melting start temperature at a temperature increase rate of 50 °C / min) / (melting start temperature at a temperature increase rate of 10 °C / min) when measuring the heat flow (mW / mg) under the conditions of a temperature increase rate of 10 °C / min and 50 °C / min is 1.00 or more and 1.10 or less, more preferably 1.00 or more and 1.08 or less, and even more preferably 1.00 or more and 1.05 or less. Also, when measuring the heat flow (mW / mg) under the condition of a temperature increase rate of 10 °C / min, the absolute value of the maximum heat flow / heat of fusion is preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.029 or more, and preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.042 or less.

[0039] <Curing catalyst> The curing catalyst disclosed in this specification may contain one or more of the above-mentioned epoxyamine adducts. It may also contain one or more other curing catalysts other than the above-mentioned epoxyamine adducts.

[0040] Other curing catalysts are not particularly limited, and examples include commercially available curing catalysts used in one-component epoxy resin adhesives, such as those in which functional groups such as amines are modified on thermoplastic resins, and those in which amine-based curing agents are covered with a polymer shell, but are not limited thereto. When the curing catalyst contains a plurality of compounds, the proportion of the above-mentioned epoxyamine adduct is not particularly limited, but is preferably 1 to 100 wt%, more preferably 10 to 100 wt%, further preferably 30 to 100 wt%, particularly preferably 50 to 100 wt%, and most preferably 70 to 100 wt% based on the total amount of the curing catalyst.

[0041] ==Resin Composition== The resin composition disclosed in this specification contains an epoxyamine adduct having the above-mentioned characteristics and an epoxy resin. The epoxyamine adduct may have any of the structural formulas (I) to (IV). The epoxy resin is not particularly limited and may be a monofunctional epoxy resin or a polyfunctional epoxy resin.

[0042] A monofunctional epoxy resin is an epoxy resin having one epoxy group and has conventionally been used for adjusting the viscosity of an epoxy resin composition as a reactive diluent. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the monofunctional epoxy resin preferably has an epoxy equivalent of 180 to 400 g / eq.

[0043] Examples of aromatic monofunctional epoxy resins include, but are not limited to, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, m-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, etc. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred.

[0044] Examples of aliphatic monofunctional epoxy resins include, but are not limited to, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate, etc.

[0045] The polyfunctional epoxy resin refers to an epoxy resin having two or more epoxy groups. Therefore, the resin composition of the present disclosure may include a bifunctional epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, etc. The polyfunctional epoxy resin is roughly classified into an aliphatic polyfunctional epoxy resin and an aromatic polyfunctional epoxy resin.

[0046] Examples of aliphatic polyfunctional epoxy resins include diepoxy resins such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; triepoxy resins such as -trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; alicyclic epoxy resins such as vinyl(3,4-cyclohexene)dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; glycidylamine-type epoxy resins such as tetraglycidyl bis(aminomethyl)cyclohexane; hydantoin-type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy resins having a silicone backbone such as -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, etc., but not limited thereto.

[0047] Among the above examples, "cyclohexane-type diglycidyl ether" means a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a cyclohexane ring as a parent structure. "Dicyclopentadiene-type diglycidyl ether" means a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure. Further, as the cyclohexane-type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferable.

[0048] An aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring such as a benzene ring. Many of the conventionally frequently used epoxy resins, such as bisphenol A type epoxy resins, are of this type. Examples of aromatic polyfunctional epoxy resins include bisphenol A type epoxy resins; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy resins; bisphenol E type epoxy resins; bisphenol S type epoxy resins; novolac type epoxy resins; tetrabromobisphenol A type epoxy resins; fluorene type epoxy resins; biphenyl aralkyl epoxy resins; diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy resins, etc., but are not limited thereto.

[0049] As the aromatic polyfunctional epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, and glycidylamine type epoxy resin are preferable, and among them, those having an epoxy equivalent of 90 to 200 g / eq are more preferable.

[0050] <Hardener> The resin composition of the present disclosure may contain one or more hardeners. In the present specification, the hardener refers to a compound that reacts with an epoxy group of an epoxy resin as the main component to form a crosslinked structure and thereby cures.

[0051] The curing agent that may be contained in the resin composition of the present disclosure is not particularly limited, but includes compounds having an active group reactive with the epoxy group of the epoxy resin. Examples of the curing agent include nitrogen-containing compounds such as amines and their derivatives; oxygen-containing compounds such as carboxylic acid-terminated polyesters, acid anhydride-based, phenolic curing agents, bisphenol A and cresol novolac, and phenol-terminated epoxy resins; and thiol compounds.

[0052] The nitrogen-containing compounds such as amines and their derivatives are not particularly limited, but include aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane; piperazine-type polyamines such as N-aminoethylpiperazine, 1,4-bis(2-amino-2-methylpropyl)piperazine; aromatic polyamines such as diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate. Commercially available products include T-12 (trade name, manufactured by Sanyo Chemical Industries, Ltd.) (amine equivalent 116), Epicure-W, Epicure-Z (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.), jER Cure (registered trademark)-W, jER Cure (registered trademark)-Z (trade names, manufactured by Mitsubishi Chemical Corporation), Kayahard A-A, Kayahard A-B, Kayahard A-S (trade names, manufactured by Nippon Kayaku Co., Ltd.), Totaamine HM-205 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Adeka Hardener EH-101 (trade name, manufactured by Adeka Corporation), Epomic Q-640, Epomic Q-643 (trade names, manufactured by Mitsui Chemicals, Inc.), DETDA80 (trade name, manufactured by Lonza), Totaamine HM-205 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.

[0053] The acid anhydride-based curing agent is not particularly limited. For example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methyl hymic anhydride, succinic anhydride substituted with an alkenyl group, glutaric anhydride, etc. can be mentioned. In particular, 3,4-dimethyl-6-(2-methyl-1-propenyl)-1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl norbornane-2,3-dicarboxylic anhydride, hydrogenated methyl nadic anhydride, succinic anhydride substituted with an alkenyl group, diethyl glutaric anhydride are preferred. The phenolic curing agent refers to monomers, oligomers, and polymers having phenolic hydroxyl groups. For example, phenol novolac resin and its alkylated or allylated products, cresol novolac resin, phenol aralkyl (including phenylene and biphenylene skeletons) resin, naphthol aralkyl resin, triphenol methane resin, dicyclopentadiene-type phenol resin, etc. can be mentioned. Among them, allylphenol novolac resin is preferred.

[0054] The thiol compounds include hydrolyzable polyfunctional thiol compounds and non-hydrolyzable polyfunctional thiol compounds.

[0055] Examples of the hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) NR1), and the like.

[0056] Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Shikoku Chemicals Corporation), (1,3,4,6-tetrakis(3-mercaptopropyl) glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemicals Corporation), 1,3,4,6-tetrakis(mercaptomethyl) glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril, pentaerythritol tripropane thiol (trade name: PEPT, manufactured by SC Organic Chemistry Co., Ltd.), pentaerythritol tetrapropane thiol, and the like.

[0057] As the non-hydrolyzable polyfunctional thiol compound, a polyfunctional thiol compound having two or more sulfide bonds in the molecule and having three or more functional groups can also be used. Examples of such thiol compounds include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18 - hexathiadecane, 9 - [2,2 - bis(mercaptomethylthio)ethyl] - 3,5,13,15 - tetrakis(mercaptomethylthio) - 1,17 - dimercapto - 2,6,8,10,12,16 - hexathiaheptadecane, 3,4,8,9 - tetrakis(mercaptomethylthio) - 1,11 - dimercapto - 2,5,7,10 - tetrathiaundecane, 3,4,8,9,13,14 - hexakis(mercaptomethylthio) - 1,16 - dimercapto - 2,5,7,10,12,15 - hexathiahexadecane, 8 - [bis(mercaptomethylthio)methyl] - 3,4,12,13 - tetrakis(mercaptomethylthio) - 1,15 - dimercapto - 2,5,7,9,11,14 - hexathiapentadecane, 4,6 - bis[3,5 - bis(mercaptomethylthio) - 7 - mercapto - 2,6 - dithiaheptylthio] - 1,3 - dithiane, 4 - [3,5 - bis(mercaptomethylthio) - 7 - mercapto - 2,6 - dithiaheptylthio] - 6 - mercaptomethylthio - 1,3 - dithiane, 1,1 - bis[4 - (6 - mercaptomethylthio) - 1,3 - dithianylthio] - 1,3 - bis(mercaptomethylthio)propane, 1 - [4 - (6 - mercaptomethylthio) - 1,3 - dithianylthio] - 3 - [2,2 - bis(mercaptomethylthio)ethyl] - 7,9 - bis(mercaptomethylthio) - 2,4,6,10 - tetrathiaundecane, 3 - [2 - (1,3 - dithietanyl)]methyl - 7,9 - bis(mercaptomethylthio) - 1,11 - dimercapto - 2,4,6,10 - tetrathiaundecane, 9 - [2 - (1,3 - dithietanyl)]methyl - 3,5,13,15 - tetrakis(mercaptomethylthio) - 1,17 - dimercapto - 2,6,8,10,12,16 - hexathiaheptadecane, 3 - [2 - (1,3 - dithietanyl)]methyl - 7,9,13,15 - tetrakis(mercaptomethylthio) - 1,17 - dimercapto - 2,4,6,10,12,16 - hexathiaheptadecane and other aliphatic polythiol compounds; 4,6 - bis[4 - (6 - mercaptomethylthio) - 1,3 - dithianylthio] - 6 - [4 - (6 - mercaptomethylthio) - 1,3 - dithianylthio] - 1,3 - dithiane, 4 - [3,4,8,9 - tetrakis(mercaptomethylthio) - 11 - mercapto - 2,5,7,10-Tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane and other polythiol compounds having a cyclic structure are mentioned.,

[0058] <Composition ratio of the resin composition> The ratio of the curing catalyst in the resin composition is not particularly limited. However, when the resin composition is an epoxy homopolymer that does not contain a curing agent, it is preferably 0.1 to 50 wt% with respect to the epoxy resin in the resin composition, more preferably 0.1 to 30 wt%, and even more preferably 0.1 to 20 wt%.,

[0059] When the resin composition contains a curing agent, it is preferably 0.01 to 10 wt% with respect to the epoxy resin in the resin composition, more preferably 0.01 to 5 wt%, and even more preferably 0.01 to 1 wt%.

[0060] <Other components of the resin composition> In addition to the main agent, curing catalyst, and curing agent, the curable composition of the present disclosure may contain, for example, those described below as needed.

[0061] ·Stabilizer In the resin composition of the present disclosure, a stabilizer can be added to improve its storage stability and extend the pot life. Various stabilizers known as stabilizers for one-component adhesives based on epoxy resin can be used, but at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is preferred.

[0062] Examples of the liquid boric acid ester compound include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyl) borate, bis(1,4,7,10-tetraoxoundecyl)(1,4,7,10,13-pentaoxotetradecyl)(1,4,7-trioxoundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like.

[0063] As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

[0064] · Filler A filler can be added to the resin composition of the present disclosure.

[0065] Specific examples of the filler include silica filler, glass filler, alumina filler, titanium oxide filler, boron nitride filler, aluminum nitride filler, talc filler, calcium carbonate filler, resin filler (for example, polytetrafluoroethylene (PTFE) filler, silicone rubber filler, etc.), conductive fillers such as silver, copper, nickel, etc. The shape is not particularly limited and may be hollow, spherical, or amorphous. Further, the filler may be surface-treated.

[0066] · Coupling agent A coupling agent can be added to the resin composition of the present disclosure. A silane coupling agent is preferable as the coupling agent, and various silane coupling agents such as epoxy-based, amino-based, vinyl-based, methacrylic-based, acrylic-based, mercapto-based can be used. These silane coupling agents may be used alone or in combination of two or more.

[0067] As silane coupling agents, for example, as silane coupling agents having an alkenyl group, vinyltrimethoxysilane (as commercial products, those manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-1003, those manufactured by Momentive Performance Materials Japan Co., Ltd.; A-171, those manufactured by Toray Dow Corning Co., Ltd.; Z-6300, those manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL XL10, those manufactured by Nippon America Trading Co., Ltd.; Silace S210, etc. can be mentioned), vinyltriethoxysilane (as commercial products, those manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-1003, those manufactured by Momentive Performance Materials Japan Co., Ltd.; A-151, those manufactured by Toray Dow Corning Co., Ltd.; Z-6519, those manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF56, those manufactured by Nippon America Trading Co., Ltd.; Silace S220, etc. can be mentioned), vinyltriacetoxysilane (as a commercial product, GENIOSIL GF62 manufactured by Asahi Kasei Wacker Silicone Co., Ltd. can be mentioned), vinyltris(2-methoxyethoxy)silane (as a commercial product, A-172 manufactured by Momentive Performance Materials Japan Co., Ltd. can be mentioned), vinylmethyldimethoxysilane (as commercial products, A-2171 manufactured by Momentive Performance Materials Japan Co., Ltd., GENIOSIL XL12 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., etc. can be mentioned), octenyltrimethoxysilane (as a commercial product, KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned), allyltrimethoxysilane (as a commercial product, Z-6825 manufactured by Toray Dow Corning Co., Ltd. can be mentioned), p-styryltrimethoxysilane (as commercial products, KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be mentioned). For example, as silane coupling agents having an acrylic group, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane (as commercial products, KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be mentioned), etc. can be mentioned, and as silane coupling agents having a methacrylic group, 3-methacryloxypropylmethyldimethoxysilane (as commercial products, KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6033 manufactured by Toray Dow Corning Co., Ltd., etc. can be mentioned), 3-methacryloxypropyltrimethoxysilane (as commercial products, KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., those manufactured by Momentive Performance Materials Japan Co., Ltd.;A-174, manufactured by Toray Dow Corning; Z-6030, manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF31, manufactured by Nippon America Trading Co., Ltd.; Silace S710, etc. can be mentioned), 3-methacryloxypropylmethyldiethoxysilane (as a commercially available product, KBE-502, manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned), 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-503, Momentive Performance Materials Japan Co., Ltd.; Y-9936 can be mentioned), methacryloxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-5803 can be mentioned), etc. can be mentioned. As a silane coupling agent having an epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (as a commercially available product, KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.; A-186, manufactured by Toray Dow Corning; Z-6043, manufactured by Nippon America Trading Co., Ltd.; Silace S530, etc. can be mentioned), 3-glycidoxypropylmethyldimethoxysilane (as a commercially available product, KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.; Z-6044, manufactured by Toray Dow Corning; Nippon America Trading Co., Ltd.; Silace S520, etc. can be mentioned), 3-glycidoxypropyltrimethoxysilane (as a commercially available product, KBM-403, Momentive Performance Materials Japan Co., Ltd.; A-187, manufactured by Toray Dow Corning; Z-6040, manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF80, manufactured by Nippon America Trading Co., Ltd., Silace S510, etc. can be mentioned), 3-glycidoxypropylmethyldiethoxysilane (as a commercially available product, KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned), 3-glycidoxypropyltriethoxysilane (as a commercially available product, KBE-403, Momentive Performance Materials Japan Co., Ltd.; A-1871, manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF82, etc. can be mentioned), glycidoxyoctyltrimethoxysilane (as a commercially available product, KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned), etc. can be mentioned. As a silane coupling agent having an amino group, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.;KBM-602, manufactured by Momentive Performance Materials Japan; A-2120, manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF-95, manufactured by Nisshō Kōji; Silace S310, etc. can be mentioned), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-603, manufactured by Momentive Performance Materials Japan; A-1120, manufactured by Momentive Performance Materials Japan; A-1122, manufactured by Toray Dow Corning; Z-6020, manufactured by Toray Dow Corning; Z-6094, manufactured by Asahi Kasei Wacker Silicone; GENIOSIL GF-91, manufactured by Nisshō Kōji; Silace S320, etc. can be mentioned), 3-aminopropyltrimethoxysilane (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-903, manufactured by Momentive Performance Materials Japan; A-1110, manufactured by Toray Dow Corning Co., Ltd.; Z-6610, manufactured by Nisshō Kōji; Silace S360, etc. can be mentioned), 3-aminopropyltriethoxysilane (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-903, manufactured by Momentive Performance Materials Japan; A-1100, manufactured by Toray Dow Corning; Z-6011, manufactured by Nisshō Kōji; Silace S330, etc. can be mentioned), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBE-9103, Silace S340, etc. manufactured by Nisshō Kōji can be mentioned), N-phenyl-3-aminopropyltrimethoxysilane (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-573, manufactured by Momentive Performance Materials Japan; Y-9669, manufactured by Toray Dow Corning; Z-6883, etc. can be mentioned), N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (As a commercially available product, it is manufactured by Nisshō Kōji; Silace XS1003 can be mentioned), hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane (As a commercially available product, it is manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-575, manufactured by Toray Dow Corning; Z-6032, manufactured by Nisshō Kōji;Examples include Silace S350, etc. Examples of silane coupling agents having an isocyanurate group include tris-(trimethoxysilylpropyl) isocyanurate (examples of commercially available products include KBM-9659 manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane (examples of commercially available products include KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.; Z-6852 manufactured by Toray Dow Corning Co., Ltd., etc.), 3-mercaptopropyltrimethoxysilane (examples of commercially available products include KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.; A-189 manufactured by Momentive Performance Materials Japan Co., Ltd.; Z-6062 manufactured by Toray Dow Corning Co., Ltd.; Silace S810 manufactured by Nippon America Trading Co., Ltd., etc.), 3-mercaptopropyltriethoxysilane (examples of commercially available products include A-1891 manufactured by Momentive Performance Materials Japan Co., Ltd.; Z-6911 manufactured by Toray Dow Corning Co., Ltd.). Examples of silane coupling agents having a ureido group include 3-ureidopropyltrialkoxysilane (an example of a commercially available product is KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane (an example of a commercially available product is A-1160 manufactured by Momentive Performance Materials Japan Co., Ltd.). Examples of silane coupling agents having a sulfide group include bis(triethoxysilylpropyl)tetrasulfide. Examples of silane coupling agents having a thioester group include 3-octanoylthio-1-propyltriethoxysilane (an example of a commercially available product is A-LINK599 manufactured by Momentive Performance Materials Japan Co., Ltd.). Examples of silane coupling agents having an isocyanate group include 3-isocyanatopropyltriethoxysilane (examples of commercially available products include KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.; A-1310 manufactured by Momentive Performance Materials Japan Co., Ltd., etc.), 3-isocyanatopropyltrimethoxysilane (an example of a commercially available product is Y-5187 manufactured by Momentive Performance Materials Japan Co., Ltd.; manufactured by Asahi Kasei Wacker Silicone Co., Ltd.;Examples include GENIOSIL GF40, etc.;

[0068] · Other additives In the resin composition of the present disclosure, other additives such as carbon black, titanium black, ion trap agents, leveling agents, antioxidants, defoamers, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, etc. can be added within the range that does not impair the object of the present invention. The type and amount of each additive are as per conventional methods.

[0069] ==Method of using the resin composition== The resin composition disclosed in this specification can be used as a one-component epoxy resin, for example, as a sealing material, filling material, dam material, conductive or insulating adhesive, die attach material, film, coating agent, shielding material, etc. for electronic components. It can also be used for other composite materials such as paints, pipe materials, tank materials, civil engineering and construction materials such as floor materials, membranes, adhesives, etc., but the usage method is not limited to these.

Examples

[0070] ==Synthesis method of the compound== Synthesis of (Compound 1) 1 - ([1,1’ - biphenyl] - 2 - yloxy) - 3 - (2 - methyl - 1H - imidazol - 1 - yl)propan - 2 - ol

Chemical formula

[0071] 2-methyl-1-H-imidazole (manufactured by Shikoku Chemicals Corporation, 150 g, 1.83 mol) was dissolved in a mixed solvent of toluene (443 mL) and methanol (121 mL) at room temperature, and the resulting solution was heated to 80 °C and refluxed with stirring. To the resulting solution, a solution of 2-{[([1,1’-biphenyl]-2-yl)oxy]methyl}oxirane (manufactured by Mitsuho Chemical Co., Ltd., 210 g, 0.913 mol, epoxy equivalent 230 g / eq) dissolved in toluene (363 mL) at room temperature was added dropwise at a rate of 3.75 mL / min. After the entire amount was added dropwise, the resulting mixture was stirred at 80 °C for 75 minutes. Then, the solvent of the resulting reaction product was distilled off at 50 °C using an evaporator to obtain a crude product (392 g). Here, the crude product obtained here is designated as Compound 1'.

[0072] The obtained crude product (380 g) was added to methanol (1514 mL), heated to 50 °C, and dissolved with stirring. Then, it was concentrated until the total amount of methanol reached 1226 mL and suction filtered. After the resulting solution was heated to 50 °C again, it was left standing for 16 hours while stirring at room temperature. The resulting suspension was suction filtered, and the filtrate was washed with pure water (600 mL × 4 times). The obtained filtrate was dried in a dryer at 40 °C for 178 hours to obtain 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol (134 g, yield 60%) as a white solid. The physical property measurement values of the product are as follows.

[0073] 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol 11H NMR (400 MHz, METHANOL-d4) δ ppm 2.15 (s, 3 H) 3.80 - 3.90 (m, 2 H) 3.95 - 4.07 (m, 3 H) 6.73 (d, 1 H) 6.81 (d, 1 H) 7.02 - 7.07 (m, 2 H) 7.28 - 7.34 (m, 3 H) 7.41 (t, 2 H) 7.50 - 7.54 (d, 2 H). HRMS (ESI) calcd for C19H20N2O2 [M+H]+ Exact Mass : 309.153, found 309.159.

[0074] (Compound 2) Synthesis of 1-[([1,1’-biphenyl]-3-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol [Chemical Structure]

[0075] First, 3-Phenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., 33.7 g, 198 mmol) and potassium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd., 35.5 g, 257 mmol) were added to Epibromohydrin (manufactured by Tokyo Chemical Industry Co., Ltd., 48.7 mL, 593 mmol), heated to 120 °C, and stirred for 4.5 hours. The resulting solution was cooled to room temperature, dichloromethane (300 mL) was added, the solid was filtered off, the solid was washed with dichloromethane, and the resulting liquid was added to the filtrate. The solvent was distilled off under reduced pressure. The obtained solid was dissolved in dichloromethane (200 mL), silica gel (150 g) was added, concentrated under reduced pressure, and the resulting solution was purified by medium-pressure column chromatography (200 g of silica gel, n-hexane / chloromethane = 50 / 50 to 35 / 65). The fraction containing the target product was recovered and concentrated to obtain 2-{[([1,1’-biphenyl]-3-yl)oxy]methyl}oxirane (37.0 g, 164 mmol) as a colorless oily substance.

[0076] Next, 2-Methyl-1H-imidazole (manufactured by Shikoku Chemicals Corporation, 40.3 g, 491 mmol) was dissolved in a mixed solvent of toluene (130 mL) and methanol (30 mL), heated to 80 °C, and a toluene (230 mL) solution of 2-{[([1,1’-biphenyl]-3-yl)oxy]methyl}oxirane (37.0 g, 164 mmol) was added dropwise over 2 hours. Then, the mixture was stirred at 80 °C for 4 hours. The resulting solution was cooled to room temperature and concentrated under reduced pressure. The obtained solid was suspended in methanol (50 mL), heated to 60 °C to dissolve it, then pure water (100 mL) was added, and after cooling to room temperature, it separated into two layers. Further, it was stirred in an ice bath, the precipitated solid was collected by filtration, washed with pure water, and dried under reduced pressure. The obtained solid was suspended in methanol (150 mL), heated to 60 °C to dissolve it, and then cooled to room temperature. The precipitated solid was collected by filtration, washed with pure water, and dried under reduced pressure to obtain 1-[([1,1’-biphenyl]-3-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol (27.8 g, yield 55%) as a colorless solid. The physical property measurement values of the product are as follows.

[0077] 1-[([1,1’-biphenyl]-3-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol 1 H NMR (400 MHz, METHANOL-d4) δ ppm 2.37 (s, 3 H) 3.95 - 3.99 (m, 2 H) 4.08 - 4.12 (m, 1 H) 4.18 - 4.24 (m, 2 H) 6.79 - 6.80 (m, 1 H) 6.92 (dd, 1 H) 7.02 - 7.03 (m, 1 H) 7.16 - 7.21 (m, 2 H) 7.29 - 7.36 (m, 2 H) 7.41 (t, 2 H) 7.58 (d, 2 H). HRMS (ESI) calcd for C19H20N2O2 [M+H]+ Exact Mass : 309.160, found 309.159.

[0078] (Compound 3) Synthesis of 1-[([1,1’-biphenyl]-4-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol

Chem.

[0079] First, 4-Phenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., 5.00 g, 29.4 mmol) and potassium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd., 5.28 g, 38.2 mmol) were added to Epibromohydrin (manufactured by Tokyo Chemical Industry Co., Ltd., 7.23 mL, 88.1 mmol), heated to 120 °C, and stirred for 3 hours. After the obtained solution was cooled to room temperature, dichloromethane (30 mL) was added, the solid was filtered off, the solid was washed with dichloromethane, and the obtained washing solution was combined with the filtrate. The obtained solution was concentrated under reduced pressure. The obtained solid was purified by medium-pressure column chromatography (100 g of silica gel, n-hexane / dichloromethane = 50 / 50 to 35 / 65), and the fraction containing the target product was collected and concentrated to obtain 2-{[([1,1’-biphenyl]-4-yl)oxy]methyl}oxirane (5.49 g, 24.3 mmol) as a colorless solid.

[0080] Next, 2-Methyl-1H-imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., 3.98 g, 48.5 mmol) was dissolved in a mixed solvent of toluene (8 mL) and methanol (4 mL). After heating to 80 °C, a toluene (35 mL) solution of 2-{[([1,1’-biphenyl]-4-yl)oxy]methyl}oxirane (5.49 g, 24.3 mmol) was added dropwise over 1 hour. Then, the mixture was stirred at 80 °C for 3.5 hours. The resulting solution was cooled to room temperature and concentrated under reduced pressure. The obtained solid was suspended in methanol (15 mL), the solid was filtered off, the solid was washed with methanol, and the resulting liquid was combined with the filtrate. The obtained solution was concentrated under reduced pressure. The obtained solid was purified by medium-pressure column chromatography (100 g of silica gel, dichloromethane / methanol = 98 / 2 to 90 / 10), and the fraction containing the target product was collected and concentrated to obtain 1-[([1,1’-biphenyl]-4-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol (4.53 g, 14.7 mmol, yield 61%) as a colorless solid. The physical property measurement values of the product are as follows.

[0081] 1-[([1,1’-biphenyl]-4-yl)oxy]-3-(2-methyl-1H-imidazole-1-yl)propan-2-ol 1 H NMR (400 MHz, METHANOL-d4) δ ppm 2.37 (s, 3 H) 3.91 - 3.99 (m, 2 H) 4.08 - 4.12 (m, 1 H) 4.16 - 4.24 (m, 2 H) 6.80 (d, 1 H) 7.00 - 7.04 (m, 3 H) 7.26 (t, 1 H) 7.38 (t, 2 H) 7.51 - 7.56 (m, 4 H). HRMS (ESI) calcd for C19H20N2O2 [M+H]+ Exact Mass : 309.160, found 309.159.

[0082] Synthesis of 1-[([1,1'-biphenyl]-2-yl)oxy]-3-(2-undecyl-1H-imidazol-1-yl)propan-2-ol (Compound 4) [Chemical formula]

[0083] 2-Undecyl-1H-imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 53.07 g, 239 mmol) was dissolved in toluene (64 mL). After heating to 80°C, a solution of 2-{[([1,1’-biphenyl]-2-yl)oxy]methyl}oxirane (manufactured by Mitsuho Chemical Co., Ltd., 30.0 g, 133 mmol) in toluene (190 mL) was added dropwise over 4.5 hours, and then the mixture was stirred at the same temperature for 4 hours. After cooling the reaction solution to room temperature, it was concentrated under reduced pressure to obtain a residue (84.4 g). The obtained residue (67.1 g) was purified by medium-pressure column chromatography (silica gel, dichloromethane / methanol = 99 / 1 to 90 / 10), and the fraction containing the target product was concentrated to obtain 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-undecyl-1H-imidazole-1-yl)propan-2-ol (35.6 g) as a colorless solid. Acetonitrile (200 mL) was added to the obtained 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-undecyl-1H-imidazole-1-yl)propan-2-ol (35.6 g), and ultrasonic waves were applied for 30 minutes by ultrasonic cleaning. The mixture was filtered, washed with acetonitrile (10 mL × 5), and the solid was dried under reduced pressure to obtain 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-undecyl-1H-imidazole-1-yl)propan-2-ol (30.8 g, 68.7 mmol, yield 65%) as a colorless solid. The physical property measurement values of the product are as follows.

[0084] 1-[([1,1’-biphenyl]-2-yl)oxy]-3-(2-undecyl-1H-imidazole-1-yl)propan-2-ol 11H NMR (400 MHz, methanol-d4) δ ppm 0.87 (t, 3 H) 1.15 - 1.30 (m, 16 H) 1.51 - 1.55 (m, 2 H) 2.46 (t, 2 H) 3.83 - 3.89 (m, 2 H) 3.94 - 4.00 (m, 2 H) 4.02 - 4.04 (m, 1 H) 6.76 (d, 1 H) 6.84 (s, 1 H) 7.01 - 7.05 (m, 2 H) 7.27 - 7.32 (m, 3 H) 7.40 (t, 2 H) 7.53 (d, 2 H). HRMS (ESI) calcd for C29H40N2O2 [M+H]+ Exact Mass : 449.316, found 449.316.

[0085] (Compound 5) Synthesis of 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol

Chem.

[0086] 2-Methyl-1H-imidazole (manufactured by Shikoku Chemicals Corporation, 21.8 g, 266 mmol) was dissolved in a mixed solvent of toluene (78.7 mL) and methanol (17.7 mL), heated to 80 °C, and a toluene (38.1 mL) solution of 2-(Phenoxymethyl)oxirane (manufactured by Nagase ChemteX Corporation, Denacol EX-141, 22.0 g, 147 mmol) was added dropwise over 1 hour. Then, the mixture was stirred at the same temperature for 1 hour. The resulting solution was cooled to room temperature, and the solvent was distilled off under reduced pressure to obtain 1-(2-methyl-1H-imidazole-1-yl)-3-phenoxypropan-2-ol (47.85 g) as a yellow solid. The product was identified by 1 1H NMR, and it was confirmed that the target product was obtained.

[0087] (Compound 6) Synthesis of α,α’-[(1-methylethylidene)bis(4,1-phenyleneoxymethylene)]bis[2-methyl-1H-imidazole-1-ethanol

Chem.

[0088] 2-Methyl-1H-imidazole (manufactured by Shikoku Chemicals Corporation, 43.8 g, 533 mmol) was dissolved in a mixed solvent of toluene (60.6 mL) and methanol (16.8 mL), the temperature was raised to 80 °C, and a toluene (83.2 mL) solution of 2,2’-{propane-2,2-diylbis[(4,1-phenylene)oxymethylene]}bis(oxirane) (manufactured by Osaka Soda Co., Ltd., 48.0 g, 133 mmol) was added dropwise over 2 hours, and then the mixture was stirred at 80 °C for 2 hours. The resulting solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and α,α’-[(1-methylethylidene)bis(4,1-phenyleneoxymethylene)]bis[2-methyl-1H-imidazole-1-ethanol (112.9 g) was obtained as a yellow solid. The product was identified by 1 1H NMR, and it was confirmed that the target product was obtained.

[0089] (Compound 7) Synthesis of 1-(2-methylimidazol-1-yl)-3-naphthalen-1-yloxypropan-2-ol

Chem.

[0090] 1H NMR (400 MHz, DMSO-d6) δ ppm 2.28 (s, 3 H), 3.98 - 4.13 (m, 3H), 4.15 - 4.27 (m, 2 H), 5.70 (bs, 1H), 6.71 (d 1.2Hz, 1 H), 6.93 (d 7.6Hz, 1 H), 7.05 (d 1.2Hz, 1H), 7.40 (dd 7.6Hz, 7.6Hz, 1 H), 7.44 - 7.56 (m, 3 H), 7.82 - 7.92 (m, 1H), 8.25-8.31 (m, 1H).

[0091] ==Properties I of the resin composition== In this example, it is shown that the resin composition containing the curing catalyst disclosed in this specification has excellent properties.

[0092] First, as a curing catalyst, Compounds 1 to 7 and 1' described in Table 1 were prepared. The structural formulas of each compound are shown in Figure 1. The synthesis methods of Compounds 1 to 7 and 1' are as described above. The melting point was measured using a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH). First, 5 mg of the synthesized compound was weighed into an aluminum pan, sealed with an aluminum lid, and then a hole was made in the center of the lid with a needle to prepare a measurement sample. Next, while maintaining a nitrogen atmosphere (100 mL / min), the heat flow (mW / mg) was measured while increasing the temperature at a rate of 10 °C / min in the range of 25 to 250 °C for this measurement sample. The temperature corresponding to the melting point and at which a peak is obtained on the graph (referred to as the melting peak temperature in this specification) was calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 6.1.0B). Clear melting peaks were obtained for Compounds 1-4 and 7 (crystalline substances), but no clear melting peaks were obtained for Compound 5 (oily) and Compound 6 (solid).

[0093]

Table 1

[0094] After grinding Compounds 1 to 7 and 1' in a mortar, they were added to EXA835LV (manufactured by DIC, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), which is an epoxy resin, while stirring by hand. The ratios of these were 12 wt% of the curing catalyst and 88 wt% of the epoxy resin. After being kneaded to some extent by stirring, they were ground in a mortar until aggregation disappeared, and then stirred and degassed under vacuum using a planetary stirring and degassing device to obtain a resin composition.

[0095] When preparing the resin composition and after storing it for 24 hours in an environment of 25°C ± 2°C and 50% RH ± 10% RH, using an E-type viscometer (TVE-25H: manufactured by Toki Sangyo Co., Ltd., rotor name: 3°×R9.7), at 5 rpm and 25°C, measure in a preset appropriate range (H, R, or U), and calculate (viscosity after 24 hours / viscosity at the time of preparation) as the pot life. The gel time was measured using a gelation tester (GT-D-15A: manufactured by Eucalyptus Giken Co., Ltd.). The hot plate was set at 120°C, and the resin composition was transferred onto the hot plate with a test bar. The time until the hardness at which the shape does not change even when touching the resin composition with the test bar was defined as the gel time. The results are shown in Table 2.

[0096]

Table 2

[0097] In this example, the characteristics were measured using compound 1', which is the crude product of compound 1, indicating that the degree of purification affects the characteristics of the resin. Note that, in this specification, the crude product refers to something that has not undergone purification processes such as recrystallization or column purification.

[0098] First, when calculating the melting peak temperature of the curing catalyst as described above, the heat flow at the peak temperature (i.e., the maximum heat flow) and the area of the peak (i.e., the heat of fusion) were analyzed using the analysis software of the device. Then, the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) was calculated.

[0099] Next, in the range of 25 to 250°C, the heat flow (mW / mg) of the curing catalyst was measured under the conditions of a heating rate of 10°C / min and a heating rate of 50°C / min. The melting start temperature (°C) under each condition was analyzed, and as the heating rate dependence, (melting start temperature at a heating rate of 50°C / min) / (melting start temperature at a heating rate of 10°C / min) was calculated (Table 2). Note that the melting start temperature is the temperature at the intersection of the tangent with the maximum gradient among the tangents of the melting peak curve and the DSC baseline on the lower temperature side than the melting peak temperature.

[0100] As shown in Fig. 2, the heat of fusion is at almost the same level regardless of purification. However, for highly purified compounds, the absolute value of the maximum heat flow / heat of fusion increases, and the dependence on the heating rate decreases. In Examples 1 to 5 (when Compounds 1 to 4 and 7 were used), where the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is large and the dependence on the heating rate is small, the viscosity hardly changed even after 24 hours from the preparation of the resin composition. However, in Comparative Example 1 (Compound 1’) where the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is small and the dependence on the heating rate is large, or in Comparative Examples 2 and 3 (Compounds 5 and 6) where no melting peak could be detected (indicated as ND in the table) and the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) and the dependence on the heating rate could not be calculated, the viscosity became so high that it could not be measured after 24 hours (indicated as UM in the table). Thus, the resin composition of the examples had a longer pot life.

[0101] Also, in Examples 1 to 5, gelation occurred at 120°C. In Comparative Examples 1 to 3, the pot life was short and could not withstand actual use, so the gel time was not measured.

[0102] Thus, compared with Compound 1’ (Comparative Example 1), which is a crude product of Compound 1, a monofunctional phenyl epoxy adduct (Comparative Example 2), and a bifunctional epoxy adduct (Comparative Example 3), the epoxyamine adduct disclosed in this specification has a good pot life and sufficient curability, so a resin composition with better properties can be obtained.

[0103] ==Properties II of Resin Composition== Examples 6 to 8 show that the resin composition containing Compound 1 and an epoxy resin has excellent properties regardless of the type of epoxy resin.

[0104] As the curing catalyst, Compound 1 was used in Examples 6 to 8. As the epoxy resins, EXA835LV (manufactured by DIC Corporation, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), YDF8170 (manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol F type epoxy resin), and CDMDG (manufactured by Showa Denko K.K., aliphatic epoxy resin) were used. The curing of these epoxy resins was carried out by homopolymerization of epoxy, a curing reaction with an acid anhydride, and a curing reaction with a phenolic compound, respectively. In addition, the pot life and gel time were measured under the same experimental conditions as in the case of Table 2, except that the heating for gel time measurement was set to 150°C.

[0105]

Table 3

[0106] As shown in Examples 6 to 8, even if the epoxy resin is an aliphatic epoxy resin or the curing agent is an acid anhydride or a phenolic resin, the epoxyamine adduct disclosed in this specification has a good pot life and can be sufficiently cured.

Industrial Applicability

[0107] According to the present invention, it has become possible to provide an epoxyamine adduct, a curing catalyst, a resin composition, a sealing material, an adhesive, and a cured product having good characteristics.

Claims

1. An epoxyamine adduct used as a curing catalyst for a thermosetting resin, wherein the epoxy resin to which the amine is adducted is a compound having one epoxy group, in differential scanning calorimetry (DSC), the value of (melting start temperature at a heating rate of 50 °C / min) / (melting start temperature at a heating rate of 10 °C / min) is 1.00 or more and 1.10 or less, the epoxyamine adduct.

2. The epoxyamine adduct according to claim 1, wherein the value of (melting start temperature at a heating rate of 50 °C / min) / (melting start temperature at a heating rate of 10 °C / min) is 1.01 or more and 1.05 or less.

3. In differential scanning calorimetry (DSC) at a heating rate of 10 °C / min, in melting, the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is 0.01 or more and 0.10 or less, the epoxyamine adduct according to claim 1 or 2.

4. The epoxyamine adduct according to claim 3, wherein the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is 0.027 or more and 0.042 or less.

5. The epoxyamine adduct according to claim 3, wherein the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is 0.029 or more and 0.042 or less.

6. The amine to be adducted is an imidazole compound, a primary amine compound or a secondary amine compound, the epoxyamine adduct according to any one of claims 1 to 5.

7. The epoxy resin to which the amine is adducted is a compound having a biphenyl skeleton or a naphthyl skeleton and having one epoxy group, the epoxyamine adduct according to any one of claims 1 to 5.

8. A curing catalyst for an epoxy resin containing the epoxyamine adduct according to any one of claims 1 to 7.

9. A resin composition containing the curing catalyst according to claim 8.

10. A sealing material containing the resin composition according to claim 9.

11. An adhesive containing the resin composition according to claim 9.

12. A cured product of the resin composition according to claim 9.

13. A method for producing the epoxyamine adduct according to any one of claims 1 to 7, comprising a step of adducting a compound having a biphenyl skeleton and having one epoxy group to an amine.

14. The method for producing an epoxyamine adduct according to any one of claims 1 to 7, comprising the step of adducting a compound having a naphthyl skeleton and having one epoxy group to an amine.

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