WO2022210190A1 - アミン誘導体 - Google Patents

アミン誘導体 Download PDF

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Publication number
WO2022210190A1
WO2022210190A1 PCT/JP2022/013647 JP2022013647W WO2022210190A1 WO 2022210190 A1 WO2022210190 A1 WO 2022210190A1 JP 2022013647 W JP2022013647 W JP 2022013647W WO 2022210190 A1 WO2022210190 A1 WO 2022210190A1
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manufactured
resin composition
mercaptomethylthio
amine derivative
epoxy
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PCT/JP2022/013647
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English (en)
French (fr)
Japanese (ja)
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友也 中井
理恵子 永田
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ナミックス株式会社
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Priority to JP2023511075A priority Critical patent/JPWO2022210190A1/ja
Publication of WO2022210190A1 publication Critical patent/WO2022210190A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to amine derivatives.
  • a one-component adhesive contains a main agent and a curing catalyst, or a main agent, a curing agent, and a curing catalyst. Cure catalysts are believed to have the greatest impact on the pot life and cure conditions of adhesives.
  • An object of the present invention is to provide a novel amine derivative.
  • 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. It is an amine derivative having a phthalimide skeleton having a ratio of 1.10 or less.
  • the value of (the melting initiation temperature at a heating rate of 50° C./min)/(the melting initiation temperature at a heating rate of 10° C./min) may be 1.00 or more and 1.01 or less.
  • the absolute value of (maximum heat flow [mW / mg]) / (heat of fusion [J / g]) is 0.01 or more and 0.10 It may be below.
  • the absolute value of (maximum heat flow [mW/mg])/(heat of fusion [J/g]) may be 0.023 or more and 0.045 or less.
  • Another embodiment of the present invention is a curing catalyst for an epoxy resin containing any of the above amine derivatives, a resin composition containing the curing catalyst, a sealing material or adhesive containing the resin composition, or It is a cured product of the resin composition.
  • a further embodiment of the present invention is any of the above methods for producing an amine derivative, comprising the step of adducting a compound having a phthalimide skeleton and one epoxy group to an amine.
  • the amine derivative is an epoxyamine adduct.
  • Amine derivatives that exhibit such skeletons and properties are useful as curing catalysts for thermosetting resins such as epoxy resins and compounds with polymerizable double bond groups (for example, (meth)acrylic compounds and maleimide compounds).
  • thermosetting resins such as epoxy resins and compounds with polymerizable double bond groups
  • (meth)acrylic compounds and maleimide compounds for example, (meth)acrylic compounds and maleimide compounds.
  • the curing catalyst and resin composition using the amine derivative according to the present invention are described below.
  • acryl and methacryl are collectively referred to as (meth)acryl.
  • the amine derivative according to one embodiment of the present invention has a long pot life and sufficient curing when used as a curing catalyst for an epoxy resin or a compound having a polymerizable double bond group ((meth)acrylic compound or maleimide compound). show gender.
  • the melting point of this amine derivative can be determined by the following procedure using, for example, a differential scanning calorimeter (DSC 204 F1 Phoenix (registered trademark)) (manufactured by NETZSCH).
  • DSC 204 F1 Phoenix (registered trademark) manufactured by NETZSCH.
  • NETZSCH differential scanning calorimeter
  • 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.
  • the heat flow mW/mg
  • the temperature at which the peak top is obtained on the graph is calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 8.0.2), and that temperature is taken as the melting point.
  • the heat flow at the melting point (that is, the maximum heat flow) and the area of the peak at the melting point (that is, the heat of fusion) are analyzed by the analysis software of the device. Then the absolute value of (maximum heat flow [mW/mg])/(heat of fusion [J/g]) can be calculated. Next, the heat flow (mW/mg) was measured in the range of 25 to 250° C. under the conditions of a heating rate of 10° C./min and a heating rate of 50° C./min, and the melting initiation temperature (° C.) under each condition was determined. Analyzed, the temperature increase rate dependence can be calculated as (melting start temperature at a temperature increase rate of 50° C./min)/(melting start temperature at a temperature increase rate of 10° C./min).
  • the temperature increase rate dependence of this amine derivative is the temperature increase rate dependence when the heat flow (mW/mg) is measured at a temperature increase rate of 10 ° C./min and 50 ° C./min.
  • the melting start temperature at 10° C./min)/(melting start temperature at a heating rate of 10° C./min) is preferably 1.00 or more and 1.10 or less, and is 1.00 or more and 1.08 or less. is more preferably 1.00 or more and 1.05 or less, even more preferably 1.00 or more and 1.02 or less, and even more preferably 1.00 or more and 1.01 or less.
  • the absolute value of the maximum heat flow/heat of fusion is preferably 0.007 or more, and preferably 0.01 or more. is more preferably 0.023 or more, preferably 0.1 or less, more preferably 0.07 or less, and even more preferably 0.045 or less.
  • the term "curing catalyst” means a catalyst having a function of promoting the initiation and/or progress of polymerization when the main agent is self-polymerized or when the main agent and the curing agent are polymerized. do.
  • the curing catalyst may be incorporated only at the terminal of the polymer.
  • R 1 is a group selected from hydrogen, phenyl and C1-C17, preferably C1-C11 alkyl
  • R 2 , R 3 , R 5 are each independently a group selected from hydrogen and C1-C6 alkyl
  • R4 is a group selected from hydrogen, OH and OAc (Ac: abbreviation for acetyl group)
  • n and m are integers, the sum of which is 1 or more and 12 or less, preferably 6 or less, More preferably, it is 3 or less.
  • the sum of n and m is 1 when R4 is hydrogen, and both n and m are 1 when R4 is OH.
  • the synthesis method includes a step of adducting a compound having a phthalimide skeleton and one epoxy group to an amine.
  • this curing catalyst has a phthalimide skeleton and satisfies the above specific parameters, the curing catalyst is less likely to dissolve in the resin in an unintended temperature range in the resin composition, resulting in a longer pot life and heat curing. It is useful as a curing catalyst for hardening resins.
  • the curing catalyst disclosed herein may contain one or more compounds having the structural formula (I). It may also contain one or more curing catalysts other than the compound having structural formula (I).
  • the resin is not particularly limited, but a thermosetting resin is preferred. Specifically, epoxy resins and compounds having a polymerizable double bond group (for example, (meth)acrylic compounds and maleimide compounds) can be exemplified.
  • Epoxy resin The epoxy resin is not particularly limited, and may be a monofunctional epoxy resin or a multifunctional epoxy resin.
  • a monofunctional epoxy resin is an epoxy resin having one epoxy group, and has been conventionally used as a reactive diluent to adjust the viscosity of an epoxy resin composition.
  • 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.
  • aromatic monofunctional epoxy resins include phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, m- Examples include, but are not limited to, phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, and the like.
  • p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred.
  • aliphatic monofunctional epoxy resins include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, ⁇ -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, neodecanoic acid glycidyl ester, etc. can be, but are not limited to:
  • a polyfunctional epoxy resin is an epoxy resin having two or more epoxy groups. Accordingly, the resin composition of the present disclosure may include difunctional epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins, and the like. Polyfunctional epoxy resins are roughly classified into aliphatic polyfunctional epoxy resins and aromatic polyfunctional epoxy resins.
  • aliphatic polyfunctional epoxy resins examples include (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether.
  • diepoxy resins such as ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether; Triepoxy resins such as methylolpropane triglycidyl ether, glycerin triglycidyl ether; vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxy Cycloaliphatic epoxy resins such as cyclohexyl)-m-dioxane; glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; h
  • cyclohexane-type diglycidyl ether means that two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as a base structure.
  • a compound having a structure is meant.
  • dicyclopentadiene-type diglycidyl ether refers to 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 base structure. means.
  • cyclohexane-type diglycidyl ether cyclohexanedimethanol diglycidyl ether is particularly preferred.
  • Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins having a structure containing aromatic rings such as benzene rings. Many conventional epoxy resins, such as bisphenol A type epoxy resin, 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; type epoxy resin; bisphenol S type epoxy resin; novolac type epoxy resin; tetrabromobisphenol A type epoxy resin; fluorene type epoxy resin; biphenyl aralkyl epoxy resin; ,3′,5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl; diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m- glycidylamine-type epoxy resins
  • aromatic polyfunctional epoxy resins bisphenol F-type epoxy resins, bisphenol A-type epoxy resins and glycidylamine-type epoxy resins are preferable, and among them, those having an epoxy equivalent of 90 to 200 g/eq are preferable.
  • the polymer compound having a polymerizable double bond group is not particularly limited.
  • compounds having an alkyl group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal Butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, etc.; compounds having cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isobornyl methacryl
  • trimethylolpropane triacrylate pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
  • Multifunctional (meth)acrylates of polyol derivatives such as; Pentaerythritol triarylate, pentaerythritol tetraarylate, trimethylolpropane triarylate and other polyfunctional arylates; Aronix M-7100, Aronix M-8030, Aronix M-8060 polyester (meth)acrylates such as Toagosei Co., Ltd.; Co., Ltd.), Aronix M-305, Aronix M-309, Aronix M-310, M-315, M-320, Aronix M-350, Aronix M-360, Aronix M-370, Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, (all manufactured by Toagosei Co., Ltd.), Neomer TA-401, TA-505, EA-301, DA-600 (both Sanyo Chemical Industries Co., Ltd.) ), NK Ester A-TMPT, NK Ester
  • compounds having a maleimide group include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'- Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl) ) methane, m-phenylenebismaleimide (N,N′-1,3-phenylenebismaleimide), 1,6-bismaleimidohexane, 1,2-bismaleimidoethane (N,N′-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyl
  • dimer acid-modified bismaleimide It is also possible to use dimer acid-modified bismaleimide.
  • dimer acid-modified bismaleimides include liquid bismaleimides BMI-689, BMI-1500 and BMI-1700, and solid bismaleimides BMI-3000 (all manufactured by Designer Molecules).
  • the resin compositions disclosed herein may contain one or more curing agents.
  • Curing agents that may be contained in the resin composition of the present disclosure are not particularly limited, but include, for example, nitrogen-containing compounds such as amines and their derivatives; , oxygen-containing compounds such as phenol-terminated epoxy resins; sulfur-containing compounds such as thiol compounds.
  • Nitrogen-containing compounds such as amines and derivatives thereof are not particularly limited, but aliphatic polyamines such as triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine, isophorone diamine.
  • Epomic Q-640 Epomic Q-643 (Mitsui Chemicals, trade name), DETDA80 (Lonza, trade name), Thothamine HM-205 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), etc. is mentioned.
  • the acid anhydride-based curing agent is not particularly limited, but for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methylhimic acid anhydride, alkenyl-substituted Succinic anhydride, glutaric anhydride and the like can be mentioned.
  • Phenolic curing agents refer to monomers, oligomers, and polymers generally having phenolic hydroxyl groups, such as phenol novolac resins and their alkylated or allylated products, cresol novolak resins, phenol aralkyl (including phenylene and biphenylene skeleton) resins, and naphthol aralkyls. Resins, triphenol methane resins, dicyclopentadiene type phenol resins, and the like. Among them, allylphenol novolac resin is preferable.
  • Thiol compounds include hydrolyzable polyfunctional thiol compounds and non-hydrolyzable polyfunctional thiol compounds.
  • hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate Nurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.) : EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manu
  • non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Shikoku Kasei Co., Ltd.), (1,3, 4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Kasei Co., Ltd.), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4 ,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercapto Propyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril,
  • non-hydrolyzable polyfunctional thiol compound it is also possible to use a trifunctional or higher polythiol compound having two or more sulfide bonds in the molecule.
  • thiol compounds include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercapto propylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7- dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, tetrakis(mercaptomethylthiomethyl) Methane
  • the ratio of the curing catalyst in the resin composition is not particularly limited, it is preferably 0.01 to 50 wt%, more preferably 0.01 to 30 wt%, relative to the thermosetting resin in the resin composition. More preferably, it is 0.01 to 20 wt%.
  • the pot life is defined as the time until the thickening ratio of the resin composition doubles from the initial value, and the pot life in the epoxy-thiol curing system is preferably 8 hours or longer, more preferably 12 hours or longer. , more preferably 24 hours or longer. Also in other curing systems, a longer pot life is preferable from the viewpoint of stability.
  • the curable composition of the present disclosure may optionally contain, for example, the following in addition to the main agent, curing catalyst, and curing agent.
  • Stabilizer A stabilizer can be added to the resin composition of the present disclosure in order to improve its storage stability and prolong its pot life.
  • Various known stabilizers can be used as stabilizers for one-component adhesives based on epoxy resins. preferable.
  • liquid borate compounds examples include 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri - n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, trioctadecylborate, tris(2 -ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentoxatetradecyl)(1,4,7-trioxaundecyl) Borane, tribenzylborate, triphenylborate,
  • aluminum chelate for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used.
  • organic acid for example, barbituric acid can be used.
  • filler A filler can be added to the resin composition of the present disclosure.
  • fillers include silica fillers, glass fillers, alumina fillers, titanium oxide fillers, boron nitride fillers, aluminum nitride fillers, talc fillers, calcium carbonate fillers, resin fillers (e.g., polytetrafluoroethylene (PTFE) fillers, silicone rubber fillers, etc.), conductive fillers such as silver, copper and nickel.
  • the shape is not particularly limited, and may be hollow, spherical, or amorphous.
  • the filler may be surface-treated.
  • Coupling agent A coupling agent can be added to the resin composition of the present disclosure.
  • the coupling agent is preferably a silane coupling agent, and various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto can be used. These silane coupling agents may be used alone or in combination of two or more.
  • Silane coupling agents include, for example, vinyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-1003, Momentive Performance Materials Japan Co., Ltd.; A -171, Dow Corning Toray Co., Ltd.; Z-6300, Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL XL10, Himi Shoji Co., Ltd.; KBE-1003, Momentive Performance Materials Japan; A-151, Dow Corning Toray; Z-6519, Asahi Kasei Wacker Silicone; GENIOSIL GF56, Himi Shoji; Sila Ace S220, etc.
  • vinyltriacetoxysilane commercially available from Asahi Kasei Wacker Silicone; GENIOSIL GF62
  • vinyltris(2-methoxyethoxy)silane commercially available from Momentive Performance Materials Japan
  • A-172 vinylmethyldimethoxysilane
  • commercially available products include Momentive Performance Materials Japan; A-2171, Asahi Kasei Wacker Silicone; GENIOSIL XL12, etc.
  • octenyltri Methoxysilane commercially available from Shin-Etsu Chemical Co., Ltd.; includes KBM-1083
  • allyltrimethoxysilane commercially available from Dow Corning Toray; includes Z-6825
  • p-styryltrimethoxysilane Commercially available products include KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents having an acrylic group include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-5103, etc.), and the like.
  • silane coupling agents having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane (commercially available products manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-502, Toray Dow Corning Co., Ltd.; Z-6033, etc.).
  • 3-methacryloxypropyltrimethoxysilane (commercially available from Shin-Etsu Chemical Co., Ltd.; KBM-503, Momentive Performance Materials Japan Co., Ltd.; A-174, Dow Corning Toray Co., Ltd.; Z-6030 , Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF31, Himi Shoji Co., Ltd.; Sila Ace S710, etc.), 3-methacryloxypropylmethyldiethoxysilane (commercially available products include Shin-Etsu Chemical Co., Ltd.; KBE-502.
  • N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-602; Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-95, Himi Shoji Co.; Sila Ace S310, etc.
  • N-2-(aminoethyl)-3-aminopropyltrimethoxysilane commercially available from Shin-Etsu Chemical KBM-603, Momentive Performance Materials Japan; A-1120, Momentive Performance Materials Japan; A-1122, Dow Corning Toray; Z-6020, Dow Toray Z-6094 manufactured by Corning Corporation; Z-6094 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.; GENIOSIL GF-91 manufactured by Himi Shoji Co.; KBM-903, manufactured by Momentive Performance Materials Japan; A-1110, manufactured by Dow Corning Toray Co.,
  • the resin composition of the present disclosure may contain other additives such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, digestive agents, etc., within a range that does not impair the object of the present invention.
  • Foaming agents, thixotropic agents, viscosity modifiers, flame retardants, coloring agents, solvents and the like can be added.
  • the type and amount of each additive are as per conventional methods.
  • the resin composition disclosed herein can be used, for example, as sealing materials and fillers for electronic components, dam materials, conductive or insulating adhesives, die attach materials, films, coating agents, shielding materials, and the like. can. In addition, it can be used for paints, composite materials such as pipe materials and tank materials, floor materials, civil engineering and construction materials such as membranes, adhesives, and the like, but the usage is not limited to these.
  • Denacol EX-731 (manufactured by Nagase ChemteX Corporation, 100 g, 0.363 mmol) was gradually added to the resulting solution over about 10 minutes. After dissolving everything, the mixture was heated to 70° C. and stirred at the same temperature for 6 hours. After cooling to room temperature, water (about 200 mL) was added and stirred to precipitate crystals. The resulting solid was suction filtered, washed twice with water and twice with IPA, and then dried to obtain compound 1 (85.7 g) (61% recovery).
  • the measured physical properties of the product are as follows.
  • 2-Methyl-1H-imidazole (manufactured by Shikoku Kasei Co., Ltd., 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 Denacol EX was prepared.
  • a toluene (38.1 mL) solution of -141 (manufactured by Nagase ChemteX Corporation, 22.0 g, 147 mmol) was added dropwise over 1 hour, followed by stirring at the same temperature for 1 hour.
  • 2-methyl-1-H-imidazole (manufactured by Shikoku Kasei Co., Ltd., 150 g, 1.83 mol) was dissolved in a mixed solvent of toluene (443 mL) and methanol (121 mL) at room temperature. and heated to reflux with stirring.
  • 2- ⁇ [([1,1′-biphenyl]-2-yl)oxy]methyl ⁇ oxirane (manufactured by Sanko Co., Ltd., 210 g, 0.913 mol, epoxy equivalent 230 g/eq) was added to toluene at room temperature. (363 mL) was added dropwise at a rate of 3.75 mL/min.
  • the temperature corresponding to the melting point and at which a peak is obtained on the graph was calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 8.0.2). Compounds 1-6 and 8 gave clear peaks, but Compound 7 did not give a clear peak.
  • the heat flow at the melting point i.e., maximum heat flow
  • the area of the peak i.e., heat of fusion
  • the heat flow (mW/mg) was measured under the conditions of a heating rate of 10°C/min and a heating rate of 50°C/min, and the melting initiation temperature (°C) under each condition was analyzed. Then, as the temperature increase rate dependence, (melting start temperature at a temperature increase rate of 50° C./min)/(melting start temperature at a temperature increase rate of 10° C./min) was calculated.
  • the melting initiation temperature is the temperature at the intersection of the tangent line with the maximum gradient among the tangent lines of the melting peak curve and the DSC baseline on the lower temperature side than the melting point.
  • Table 1 shows the evaluation results of the compound (curing catalyst).
  • Epoxy-thiol curing system Compounds 1 to 4, 6, 7, and 8 as curing catalysts were put into EXA835LV (manufactured by DIC), which is an epoxy resin, and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. Then, EXA835LV or a mixture of EXA835LV and CDMDG (manufactured by Showa Denko KK) was added and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device.
  • EXA835LV manufactured by DIC
  • CDMDG manufactured by Showa Denko KK
  • PEMP manufactured by SC Organic Chemical Co., Ltd.
  • SC Organic Chemical Co., Ltd. which is a thiol resin
  • stirring and defoaming were performed under vacuum to obtain a resin composition.
  • Epoxy-thiol curing system Compound 1 as a curing catalyst was added to a mixture obtained by dispersing EXA835LV and TS720 (manufactured by Cabot Specialty Chemicals) using a three-roll mill and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. C3TSG (manufactured by Shikoku Kasei Kogyo Co., Ltd.), which is a thiol resin, was added thereto and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
  • EXA835LV and TS720 manufactured by Cabot Specialty Chemicals
  • Epoxy homopolymerization curing system > Compounds 1, 5 and 6 as curing catalysts were put into EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus to obtain a resin composition.
  • Epoxy-acid anhydride curing system Compound 1 as a curing catalyst was put into EXA835LV, which is an epoxy resin, and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming apparatus. Then, YDF8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device.
  • EXA835LV an epoxy resin
  • Epoxy-phenol curing system > Compound 1 as a curing catalyst was added to EXA835LV and mixed. Thereafter, the mixture was ground in a mortar until no aggregation occurred, and stirred and defoamed under vacuum using a planetary stirring and defoaming device. EXA835LV was put in there and mixed. Thereafter, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device. Furthermore, MEH8005 (manufactured by Meiwa Kasei Co., Ltd.), which is a phenolic resin, was added and mixed. Then, using a planetary stirring and defoaming device, stirring and defoaming were performed under vacuum to obtain a resin composition.
  • MEH8005 manufactured by Meiwa Kasei Co., Ltd.
  • Acrylic-thiol curing system > M7100 (manufactured by Toagosei Co., Ltd.) as an acrylic resin, OMNIRAD184 (manufactured by IGM resins B.V.) as a photoradical generator, Q-1301 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, and a stabilizing agent.
  • TS720 was dispersed with a three-roll mill as a component, and compound 1 as a curing catalyst was added to the resulting mixture and further dispersed with a three-roll mill. After PEMP was added thereto and mixed, stirring and defoaming were performed under vacuum using a planetary stirring and defoaming device to obtain a resin composition.
  • the time before gelation (referred to as gel time) was measured using a gelation tester (GT-D-15A: manufactured by Eucalyptus Giken Co., Ltd.).
  • a hot plate was set to 100° C., 120° C., or 150° C., and the resin composition was transferred onto the hot plate using a test rod.
  • the gel time was defined as the time from touching the resin composition with a test rod until it became stringy.
  • the resin composition in the example gelled within 10 minutes and had sufficient reactivity and curability.
  • the curing catalyst of the present disclosure can be used not only in epoxy-thiol curing systems, but also in epoxy homopolymerization systems, epoxy-acid anhydride systems, epoxy-phenol systems, and acrylate-thiol systems. is.
  • the curing catalyst of the present disclosure has a phthalimide skeleton, so it has high crystallinity and a higher melting point than conventional adducts obtained by adding an epoxy resin and an imidazole derivative. , a resin composition which is stable, hardly causes the curing catalyst to dissolve in the resin at an unintended temperature, and has a long pot life can be obtained.
  • the present invention has made it possible to provide novel amine derivatives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Indole Compounds (AREA)
PCT/JP2022/013647 2021-03-30 2022-03-23 アミン誘導体 WO2022210190A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379685A (en) * 1964-08-31 1968-04-23 Ciba Ltd Curable epoxy compound composition of matter
US4619941A (en) * 1984-11-19 1986-10-28 American Cyanamid Company N-[(1H-imidazol-1-yl)alkyl]-1H-indolecarboxamides useful as thromboxane synthetase inhibitors and antihypertensive agents
WO1988008840A1 (fr) * 1987-05-04 1988-11-17 Centre National De La Recherche Scientifique (Cnrs Agents de ciblage antitumoraux, leur preparation et applications
JPH10218859A (ja) * 1997-02-04 1998-08-18 Shikoku Chem Corp トリメリットイミド誘導体およびその製造方法
WO2014104272A1 (ja) * 2012-12-28 2014-07-03 日本臓器製薬株式会社 ケイ皮酸アミド誘導体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379685A (en) * 1964-08-31 1968-04-23 Ciba Ltd Curable epoxy compound composition of matter
US4619941A (en) * 1984-11-19 1986-10-28 American Cyanamid Company N-[(1H-imidazol-1-yl)alkyl]-1H-indolecarboxamides useful as thromboxane synthetase inhibitors and antihypertensive agents
WO1988008840A1 (fr) * 1987-05-04 1988-11-17 Centre National De La Recherche Scientifique (Cnrs Agents de ciblage antitumoraux, leur preparation et applications
JPH10218859A (ja) * 1997-02-04 1998-08-18 Shikoku Chem Corp トリメリットイミド誘導体およびその製造方法
WO2014104272A1 (ja) * 2012-12-28 2014-07-03 日本臓器製薬株式会社 ケイ皮酸アミド誘導体

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