WO2016024471A1 - アルミニウムキレート系潜在性硬化剤及びその製造方法 - Google Patents

アルミニウムキレート系潜在性硬化剤及びその製造方法 Download PDF

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WO2016024471A1
WO2016024471A1 PCT/JP2015/071073 JP2015071073W WO2016024471A1 WO 2016024471 A1 WO2016024471 A1 WO 2016024471A1 JP 2015071073 W JP2015071073 W JP 2015071073W WO 2016024471 A1 WO2016024471 A1 WO 2016024471A1
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curing agent
aluminum chelate
epoxy resin
compound
latent curing
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PCT/JP2015/071073
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English (en)
French (fr)
Japanese (ja)
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和伸 神谷
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デクセリアルズ株式会社
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Priority to CN201580035642.8A priority Critical patent/CN106661201B/zh
Priority to KR1020167033928A priority patent/KR102339438B1/ko
Publication of WO2016024471A1 publication Critical patent/WO2016024471A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/70—Chelates
    • 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
    • C08G59/188—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 using encapsulated compounds
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds

Definitions

  • the present invention relates to an aluminum chelate latent curing agent in which an aluminum chelate curing agent is held by a cationic emulsion polymerization porous epoxy resin that is a polymer capsule material.
  • Patent Document 1 a microcapsule type aluminum chelate-based latent curing agent in which an aluminum chelate-based curing agent is held in a porous resin obtained by interfacial polymerization of a polyfunctional isocyanate compound as a curing agent that exhibits low-temperature rapid curing activity for epoxy resins ( Patent Document 1) has been proposed.
  • a thermosetting epoxy resin composition in which this aluminum chelate-based latent curing agent, a silane coupling agent, and an epoxy resin are blended, when a polymerization (curing) reaction is initiated by heating, it is generated from the silane coupling agent.
  • the silanolate anion was added to the ⁇ -position carbon of the epoxy group of the glycidyl ether type epoxy compound, resulting in a polymerization termination reaction. It was necessary to use a cyclic epoxy compound.
  • polyfunctional isocyanate compounds are interfacially polymerized as an aluminum chelate-based latent curing agent that can quickly cure glycidyl ether type epoxy compounds at low temperatures without using alicyclic epoxy compounds, and at the same time, the presence of radical polymerization initiators
  • a porous resin as a polymer capsule material obtained by radical polymerization of a polyfunctional radically polymerizable compound under the same condition was allowed to simultaneously hold an aluminum chelate curing agent and a specific silanol compound having a highly sterically hindered chemical structure.
  • An aluminum chelate-based latent curing agent has been proposed (Patent Document 2).
  • the polymerization termination reaction can be suppressed and a cationic active species can be formed with the aluminum chelate-based curing agent, so that the glycidyl ether type epoxy compound can be cured at a low temperature at a certain level. Can be made.
  • the low-temperature rapid curing ability of the aluminum chelate-based latent curing agent disclosed in Patent Document 2 is the glass transition point of a polymer capsule material made of an isocyanate interfacially polymerized porous resin that is considered to be most cured on the outside. Therefore, there is a problem that it is difficult to make the exothermic peak temperature at the time of thermosetting the glycidyl ether type epoxy compound 120 ° C. or lower, preferably 80 ° C. or lower.
  • An object of the present invention is to provide an aluminum chelate-based latent curing agent capable of lowering an exothermic peak temperature when thermosetting a glycidyl ether type epoxy resin to 120 ° C. or lower, preferably 80 ° C. or lower. is there.
  • the present inventor believes that the property as a polymer capsule material of a cationic emulsion polymerization porous epoxy resin obtained by cationic emulsion polymerization while receiving polymerization inhibition due to moisture in the polymerization system is that the cationic emulsion polymerization porous epoxy resin itself.
  • the object of the present invention can be achieved by using such a cationic emulsion polymerization porous epoxy resin as a polymer capsule material that develops latent potential in an aluminum chelate latent curing agent, and has completed the present invention.
  • the present invention provides an aluminum chelate-based latent material characterized in that an aluminum chelate-based curing agent and a di- or triarylsilanol compound are held in a cationic emulsion polymerization porous epoxy resin that is a polymer capsule material.
  • a hardener is provided.
  • a preferable cationic emulsion polymerization porous epoxy resin is an aqueous phase containing a dispersant, an oil phase in which an aluminum chelate curing agent, a di- or triarylsilanol compound, and an epoxy compound are dissolved or dispersed in an organic solvent. It was obtained by cationic emulsion polymerization.
  • the present invention is also a method for producing the above-mentioned aluminum chelate-based latent curing agent, wherein an oil phase obtained by dissolving or dispersing an aluminum chelate-based curing agent, a di- or triarylsilanol compound, and an epoxy compound in an organic solvent is used.
  • Cation emulsion polymerization in an aqueous phase containing a dispersing agent, and a cationic capsule polymerization porous epoxy resin which is a polymer capsule material obtained thereby holds an aluminum chelate curing agent and a di- or triarylsilanol compound
  • a manufacturing method is provided.
  • thermosetting epoxy resin composition containing the above-described aluminum chelate-based latent curing agent, an epoxy resin, and a di- or triarylsilanol compound.
  • the mechanical strength of the surface and the solvent resistance are reduced due to polymerization inhibition by moisture. ing.
  • the aluminum chelate-based latent curing agent shows potential, the epoxy compound penetrates into the capsule wall by heating, or the aluminum chelate-based curing agent exudes from the capsule wall, so that the thermal activity And low temperature rapid curability can be realized.
  • the silanol compound having a specific highly sterically hindered chemical structure is retained (in other words, protected) by the cationic emulsion polymerization porous epoxy resin, the polymerization termination reaction can be suppressed, and an aluminum chelate curing agent and Cationic active species can be formed. Therefore, in the thermosetting epoxy resin composition containing the aluminum chelate-based latent curing agent of the present invention, the glycidyl ether type epoxy resin is used as an epoxy resin at an exothermic peak temperature of 120 ° C. or lower, preferably 80 ° C. or lower. It can be cured at low temperature and high speed.
  • FIG. 2 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 1.
  • FIG. 3 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 2.
  • FIG. 4 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 3.
  • FIG. 4 is an electron micrograph (magnification: 10000 times) of the aluminum chelate-based latent curing agent of Example 3.
  • 4 is an electron micrograph (magnification: 15000 times) of the aluminum chelate-based latent curing agent of Example 3.
  • 2 is a DSC chart of a thermosetting epoxy resin composition containing the aluminum chelate-based latent curing agent of Examples 1 to 3.
  • 6 is a DSC chart of a thermosetting epoxy resin composition containing the aluminum chelate-based latent curing agent of Examples 3 to 5.
  • 6 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 6.
  • FIG. 6 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 7.
  • FIG. 6 is a particle size distribution diagram of an aluminum chelate-based latent curing agent of Example 8.
  • FIG. 6 is a DSC chart of a thermosetting epoxy resin composition containing the aluminum chelate-based latent curing agent of Examples 3 and 6 to 8.
  • the aluminum chelate-based latent curing agent of the present invention is one in which an aluminum chelate-based curing agent and a di- or triarylsilanol compound are held in a cationic emulsion polymerization porous epoxy resin that is a polymer capsule material. . More specifically, it is not a microcapsule with a simple structure in which the core of an aluminum chelate curing agent is coated with a shell of a cationic emulsion polymerization porous epoxy resin, but is present in a cationic emulsion polymerization porous epoxy resin matrix.
  • the aluminum chelate-based curing agent and the di- or triarylsilanol compound are held in a large number of fine holes.
  • the aluminum chelate-based latent curing agent of the present invention is produced using a cationic emulsion polymerization method, its shape is spherical, and its particle size is preferably 0.1 from the viewpoint of curability and dispersibility.
  • the pore size is preferably 0.1 to 50 nm from the viewpoint of curability and latency.
  • the aluminum chelate-based latent curing agent has a tendency to decrease if the crosslinking degree of the cationic emulsion polymerization porous epoxy resin to be used is too small, and if it is too large, its thermal responsiveness tends to decrease.
  • the degree of crosslinking of the cationic emulsion polymerization porous epoxy resin can be measured by a micro compression test.
  • the aluminum chelate-based latent curing agent does not substantially contain an organic solvent used in the cationic emulsion polymerization, specifically, 1 ppm or less.
  • the content of the aluminum chelate curing agent with respect to 100 parts by mass of the cationic emulsion polymerization porous epoxy resin in the aluminum chelate latent curing agent of the present invention is to realize good curability and good latency.
  • the amount is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass.
  • the content of the di- or triarylsilanol compound is also preferably 10 to 200 parts by mass, more preferably 50 to 150 parts by mass, in order to achieve good curability and good latency.
  • the cationic emulsion polymerization porous epoxy resin that is a polymer capsule material constituting the aluminum chelate-based latent curing agent of the present invention is preferably an organic compound comprising an aluminum chelate-based curing agent, a di- or triarylsilanol compound, and an epoxy compound.
  • An oil phase dissolved or dispersed in a solvent is obtained by cationic emulsion polymerization in an aqueous phase containing a dispersant.
  • This cationic emulsion polymerization is significant as a method for producing the aluminum chelate-based latent curing agent of the present invention.
  • the aluminum chelate-based latent curing agent of the present invention includes an aqueous phase containing a dispersant, an oil phase in which an aluminum chelate-based curing agent, a di- or triarylsilanol compound, and an epoxy compound are dissolved or dispersed in an organic solvent. It can be produced by emulsifying polymerization in the polymer, and retaining the aluminum chelate curing agent and the di- or triarylsilanol compound in a cationic emulsion polymerization porous epoxy resin which is a polymer capsule material obtained thereby.
  • the aluminum chelate curing agent functions as a curing agent that cationically polymerizes the epoxy compound in cooperation with the silanol compound, and forms a polymer capsule material by cationic emulsion polymerization of the blended epoxy compound.
  • Examples of such an aluminum chelate-based curing agent include complex compounds in which three ⁇ -keto enolate anions are represented by the formula (1) and coordinated to aluminum.
  • R 1 , R 2 and R 3 are each independently an alkyl group or an alkoxyl group.
  • the alkyl group include a methyl group and an ethyl group.
  • the alkoxyl group include a methoxy group, an ethoxy group, and an oleyloxy group.
  • aluminum chelate curing agent represented by the formula (1) examples include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), and aluminum monoacetyl.
  • aluminum tris acetylacetonate
  • aluminum tris ethylacetoacetate
  • aluminum monoacetylacetonate bis ethylacetoacetate
  • aluminum monoacetyl aluminum monoacetyl.
  • examples include acetonate bisoleyl acetoacetate, ethyl acetoacetate aluminum diisopropylate, and alkyl acetoacetate aluminum diisopropylate.
  • the di- or triarylsilanol compound is a highly sterically hindered silanol compound having a chemical structure of the following formula (A), unlike a conventional silane coupling agent having a trialkoxy group.
  • m is 2 or 3, preferably 3, provided that the sum of m and n is 4. Therefore, the silanol compound of the formula (A) becomes a mono or diol form.
  • “Ar” is an optionally substituted aryl group, and examples of the aryl group include a phenyl group, a naphthyl group (for example, 1 or 2-naphthyl group), an anthracenyl group (for example, 1, 2, or 9-anthracenyl group).
  • Benz [a] -9-anthracenyl group phenaryl group (eg 3 or 9-phenaryl group), pyrenyl group (eg 1-pyrenyl group), azulenyl group, fluorenyl group, biphenyl group (eg 2,3 Or 4-biphenyl group), thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyridyl group, and the like.
  • a phenyl group is preferable from the viewpoint of availability and cost.
  • the m Ars may be the same or different, but are preferably the same from the viewpoint of availability.
  • aryl groups can have 1 to 3 substituents such as halogen (chloro, bromo, etc.), trifluoromethyl, nitro, sulfo, carboxyl, alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), Electron-withdrawing groups such as formyl, electron donors such as alkyl (methyl, ethyl, propyl, etc.), alkoxy (methoxy, ethoxy, etc.), hydroxy, amino, monoalkylamino (monomethylamino, etc.), dialkylamino (dimethylamino, etc.) Group and the like.
  • substituents such as halogen (chloro, bromo, etc.), trifluoromethyl, nitro, sulfo, carboxyl, alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), Electron-withdrawing groups such as formyl, electron donors such as alkyl
  • the acidity of the hydroxyl group of silanol can be increased by using an electron withdrawing group as a substituent, and conversely, the acidity can be lowered by using an electron donating group, so that the curing activity can be controlled.
  • the substituents may be different for each of the m Ars, but the substituents are preferably the same for the m Ars from the viewpoint of availability. Further, only some Ar may have a substituent, and other Ar may not have a substituent.
  • phenyl group having a substituent examples include 2,3 or 4-methylphenyl group; 2,6-dimethyl, 3,5-dimethyl, 2,4-dimethyl, 2,3-dimethyl, 2,5- Examples include dimethyl or 3,4-dimethylphenyl group; 2,4,6-trimethylphenyl group; 2 or 4-ethylphenyl group.
  • triphenylsilanol or diphenylsilanediol is preferable. Particularly preferred is triphenylsilanol.
  • an epoxy compound constituting a porous epoxy resin a glycidyl ether type epoxy that could not be used in a mixed system of an aluminum chelate latent curing agent and a silanol compound conventionally. Resins can be preferably used.
  • Such a glycidyl ether type epoxy resin may be liquid or solid, and preferably has an epoxy equivalent of usually about 100 to 4000 and having two or more epoxy groups in the molecule.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, ester type epoxy resin and the like
  • bisphenol A type epoxy resins can be preferably used from the viewpoint of resin characteristics.
  • These epoxy resins also include prepolymers such as monomers and oligomers.
  • an alicyclic epoxy resin can also be used in the range which does not impair the effect of this invention.
  • an oxetane compound in addition to the above-described epoxy compound, can be used in combination in order to sharpen the exothermic peak.
  • Preferred oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, 4,4′-bis [(3-ethyl- 3-Oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl) methyl] ester, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- ⁇ [3- (triethoxysilyl) propoxy] methyl ⁇ oxetane, oxetanylsilsesquioxane, Phenol
  • the organic solvent constituting the oil phase is an aluminum chelate-based curing agent, a di- or triarylsilanol compound, and a good solvent for each of the epoxy compounds (the respective solubility is preferably 0.1 g / ml (organic solvent) or more).
  • a volatile organic solvent which does not substantially dissolve in water is 0.5 g / ml (organic solvent) or less
  • has a boiling point of 30 to 100 ° C. under atmospheric pressure is preferable.
  • volatile organic solvents include alcohols, acetate esters, ketones and the like. Among them, acetates, particularly ethyl acetate is preferable in terms of high polarity, low boiling point, and poor water solubility.
  • the amount of the volatile organic solvent used is such that the particle size and curing characteristics are not polydispersed with respect to the total amount of 100 parts by mass of the aluminum chelate curing agent, di- or triarylsilanol compound, and epoxy compound, and the curing characteristics are adjusted.
  • the amount is preferably 10 to 500 parts by mass, more preferably 20 to 200 parts by mass, so as not to decrease.
  • the viscosity of the oil phase solution can be lowered by using a relatively large amount of the volatile organic solvent within the amount of volatile organic solvent used.
  • the oil phase droplets in the reaction system can be made finer and more uniform, and the resulting latent hardener particle size can be controlled to submicron to several microns.
  • the particle size distribution can be monodispersed.
  • the viscosity of the oil phase solution is preferably set to 1 to 500 mPa ⁇ s.
  • the content of the di- or triarylsilanol compound with respect to 100 parts by mass of the aluminum chelate-based curing agent is preferably 5 to 500 parts by mass, more preferably, in order to realize latent curing by cationic emulsion polymerization and low-temperature fast curing properties. 20 to 200 parts by mass.
  • the amount of the epoxy compound is preferably 5 to 500 parts by mass, more preferably 20 to 200 parts by mass, in order to realize latent suppression by cationic emulsion polymerization and to suppress the decrease in curing characteristics.
  • the aqueous phase for emulsion polymerization of an oil phase in which an aluminum chelate-based curing agent, a di- or triarylsilanol compound and an epoxy compound are dissolved or dispersed in an organic solvent contains a known emulsifier.
  • Known emulsifiers include alkylbenzene sulfonate, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, soybean / yolk yolk lecithin, kirayasaponin, sodium caseinate and the like.
  • dispersants such as polyvinyl alcohol, carboxymethyl cellulose, and gelatin can be used in combination.
  • the amount of the emulsifier used is usually 0.001 to 10.0% by mass of the aqueous phase.
  • the blending amount of the oil phase with respect to the aqueous phase is preferably 5 to 90 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the aqueous phase in order to prevent polydispersion of the oil phase droplets and to prevent aggregation due to refinement. Is 10 to 70 parts by mass.
  • stirring conditions such that the size of the oil phase is preferably 0.5 to 30 ⁇ m are usually obtained at a temperature of 30 to 80 at atmospheric pressure.
  • the conditions for heating and stirring can be given at 0 ° C. and stirring time of 2 to 12 hours.
  • the polymer fine particles are filtered off and air-dried or vacuum-dried to obtain an aluminum chelate-based latent curing agent that can be used in the present invention.
  • the aluminum chelate latent curing agent is changed. It is possible to control the curing ability. For example, when the cationic emulsion polymerization temperature is lowered, the exothermic peak temperature can be lowered, and conversely, when the cationic emulsion polymerization temperature is raised, the exothermic peak temperature can be raised.
  • an aluminum chelate-based curing agent is also present on the surface, but it is inactivated by water present in the polymerization system during cationic emulsion polymerization, Only the aluminum chelate curing agent retained inside the porous resin retains activity, and the resulting curing agent is considered to have acquired the potential.
  • the aluminum chelate-based latent curing agent of the present invention is a low-temperature fast-curing thermosetting epoxy resin composition having an exothermic peak temperature of about 80 ° C. or lower by adding a di- or triarylsilanol compound to an epoxy resin. Can be provided. Such a thermosetting epoxy resin composition is also part of the present invention.
  • the content of the aluminum chelate-based latent curing agent in the thermosetting epoxy resin composition of the present invention is sufficient to cure the resin composition and have good mechanical properties (for example, flexibility) in the cured product. Is 1 to 70 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the epoxy resin.
  • the epoxy resin the epoxy compound demonstrated previously, Preferably a glycidyl ether type epoxy compound can be used.
  • the content of the di- or triarylsilanol compound in the thermosetting epoxy resin composition of the present invention is 1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin. If it is this range, it will not become inadequate hardening and the fall of the resin characteristic after hardening can be suppressed.
  • the di- or triarylsilanol compound the di- or triarylsilanol compound described above, preferably triphenylsilanol or diphenylsilanol can be used.
  • thermosetting epoxy resin composition of the present invention can further contain a silane coupling agent, a filler such as silica and mica, a pigment, an antistatic agent, and the like, if necessary.
  • the silane coupling agent is a thermosetting resin (for example, a thermosetting epoxy resin) in cooperation with an aluminum chelate curing agent.
  • a thermosetting resin for example, a thermosetting epoxy resin
  • silane coupling agent one having 1 to 3 lower alkoxy groups in the molecule, a group having reactivity with the functional group of the thermosetting resin in the molecule, such as a vinyl group, It may have a styryl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an amino group, a mercapto group, and the like.
  • a coupling agent having an amino group or a mercapto group should be used when the latent curing agent of the present invention is a cationic curing agent, so that the amino group or mercapto group does not substantially trap the generated cationic species. Can do.
  • silane coupling agents include vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -styryltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - Acryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ⁇ - (aminoethyl) ) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropy
  • the amount is 1 to 300 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the chelate-based latent curing agent.
  • thermosetting epoxy resin composition of the present invention uses an aluminum chelate-based latent curing agent as a curing agent.
  • an aluminum chelate-based latent curing agent as a curing agent.
  • it contains a glycidyl ether type epoxy compound that could not be sufficiently cured with an aluminum chelate latent curing agent
  • a highly sterically hindered silanol compound is an aluminum chelate latent curing agent. Since it is contained without impairing the ability of accelerating the cationic polymerization catalyst, the thermosetting epoxy resin composition can be subjected to low-temperature fast-curing cationic polymerization with an exothermic peak on the order of 80 ° C. or lower.
  • Example 1 (Production of aluminum chelate-based latent curing agent) 800 parts by weight of distilled water, 0.05 part by weight of a surfactant (Nurex R, NOF Corporation), 4 parts by weight of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) as a dispersant, The mixture was placed in a 3 liter interfacial polymerization vessel equipped with a meter and mixed uniformly to prepare an aqueous phase.
  • a surfactant Nurex R, NOF Corporation
  • PVA-205 polyvinyl alcohol
  • the polymerization reaction solution was allowed to cool to room temperature, and the polymer particles were filtered off and air dried to obtain 90 parts by mass of a spherical aluminum chelate-based latent curing agent.
  • the particle size distribution of volume conversion was measured using the laser type particle size distribution measuring apparatus (MT3300EXII, Nikkiso Co., Ltd.). The obtained results are shown in FIG. From this result, it can be seen that this aluminum chelate-based latent curing agent is controlled to a single micron size.
  • Example 2 (Production of aluminum chelate-based latent curing agent) 70 parts by mass of a spherical aluminum chelate-based latent curing agent was obtained in the same manner as in Example 1 except that glycidyl ether type epoxy resin (EP828, Mitsubishi Chemical Corporation) was reduced from 100 parts by mass to 80 parts by mass. Obtained. About the obtained aluminum chelate type
  • glycidyl ether type epoxy resin EP828, Mitsubishi Chemical Corporation
  • Example 3 (Production of aluminum chelate-based latent curing agent) 50 parts by weight of a spherical aluminum chelate-based latent curing agent was obtained in the same manner as in Example 1 except that glycidyl ether type epoxy resin (EP828, Mitsubishi Chemical Corporation) was reduced from 100 parts by weight to 60 parts by weight. Obtained. About the obtained aluminum chelate type
  • this aluminum chelate-based latent curing agent is controlled to a single micron size. Moreover, it turns out that the shape of an aluminum chelate type
  • curing agent is a substantially spherical shape.
  • thermosetting epoxy resin composition 4 parts by mass of the aluminum chelate-based latent curing agent of Example 1, 2 or 3, 80 parts by mass of a bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), and 8 parts by mass of triphenylsilanol are uniformly mixed.
  • a thermosetting epoxy resin composition was prepared.
  • the obtained thermosetting epoxy resin composition was subjected to thermal analysis using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments Inc.). The obtained results are shown in Table 1 and FIG.
  • the exothermic start temperature means the curing start temperature
  • the exothermic peak temperature means the temperature at which curing is most active
  • the exothermic end temperature is the curing It means the end temperature
  • the total calorific value is practically desired to be 250 J / g or more in order to achieve good low temperature fast curability.
  • EP828 blending amount (part by mass) in Table 1 is that of glycidyl ether type epoxy resin (EP828, Mitsubishi Chemical Corporation) with respect to 100 parts by mass of the aluminum chelate-based curing agent at the time of preparing the aluminum chelate-based latent curing agent. It means the blending amount (parts by mass) and is not the blending amount of the glycidyl ether type epoxy resin used when preparing the thermosetting epoxy resin composition.
  • the aluminum chelate-based latent curing agents of Examples 1 to 3 have an exothermic onset temperature of 70 ° C. or lower and an exothermic peak temperature of about 120 ° C. or lower.
  • the heat generation start temperature is about 50 ° C.
  • the exothermic peak temperature is also in the 80 ° C. range, and it can be seen that the low temperature rapid curability is improved.
  • Example 4 An aluminum chelate latent curing agent was prepared in the same manner as in Example 3 except that the cationic emulsion polymerization temperature was changed from 60 ° C. to 70 ° C., and a thermosetting epoxy resin composition was further prepared.
  • Example 5 An aluminum chelate latent curing agent was prepared in the same manner as in Example 3 except that the cationic emulsion polymerization temperature was changed from 60 ° C. to 80 ° C., and a thermosetting epoxy resin composition was further prepared.
  • thermosetting epoxy resin composition was prepared by thermal analysis using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments Inc.) as in Example 3. The obtained results are shown in Table 2 and FIG. The results of Example 3 are also shown.
  • DSC differential thermal analyzer
  • Example 6 Example 3 except that bisphenol F type epoxy resin (EP807, Mitsubishi Chemical Corporation) is used as the glycidyl ether type epoxy resin instead of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation). Similarly, an aluminum chelate-based latent curing agent was prepared.
  • bisphenol F type epoxy resin EP807, Mitsubishi Chemical Corporation
  • glycidyl ether type epoxy resin EP828, Mitsubishi Chemical Corporation
  • an aluminum chelate-based latent curing agent was prepared.
  • Example 7 Example 3 except that a phenol novolac type epoxy resin (EP152, Mitsubishi Chemical Corporation) is used instead of a bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation) as a glycidyl ether type epoxy resin. Similarly, an aluminum chelate-based latent curing agent was prepared.
  • a phenol novolac type epoxy resin EP152, Mitsubishi Chemical Corporation
  • a bisphenol A type epoxy resin EP828, Mitsubishi Chemical Corporation
  • an aluminum chelate-based latent curing agent was prepared.
  • Example 8 Example 3 except that dicyclopentadiene type epoxy resin (EP4088S, ADEKA Corporation) is used as the glycidyl ether type epoxy resin instead of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation). Similarly, an aluminum chelate-based latent curing agent was prepared.
  • dicyclopentadiene type epoxy resin EP4088S, ADEKA Corporation
  • bisphenol A type epoxy resin EP828, Mitsubishi Chemical Corporation
  • thermosetting epoxy resin composition 4 parts by mass of the aluminum chelate-based latent curing agent of Examples 3 and 6 to 8, 80 parts by mass of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation), and 8 parts by mass of triphenylsilanol are uniformly mixed.
  • a thermosetting epoxy resin composition was prepared and subjected to thermal analysis using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments Inc.) in the same manner as in Example 3. The obtained results are shown in Table 4 and FIG. The results of Example 3 are also shown for reference.
  • DSC differential thermal analyzer
  • the heat generation start temperature can be set to 50 ° C. or lower, and the heat generation peak temperature can be set to 80 ° C. Recognize.
  • the aluminum chelate-based latent curing agent of the present invention is useful as a latent curing agent for glycidyl ether type epoxy adhesives for low-temperature short-time connection.

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  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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WO2022138120A1 (ja) * 2020-12-21 2022-06-30 デクセリアルズ株式会社 硬化剤及びその製造方法、並びに硬化用組成物

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