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WO2019069866A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2019069866A1
WO2019069866A1 PCT/JP2018/036732 JP2018036732W WO2019069866A1 WO 2019069866 A1 WO2019069866 A1 WO 2019069866A1 JP 2018036732 W JP2018036732 W JP 2018036732W WO 2019069866 A1 WO2019069866 A1 WO 2019069866A1
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WO
WIPO (PCT)
Prior art keywords
meth
group
curable composition
polymer
acrylate
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English (en)
Japanese (ja)
Inventor
聖 宮藤
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Kaneka Corp
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Kaneka Corp
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Priority to JP2019546702A priority Critical patent/JP7246313B2/ja
Publication of WO2019069866A1 publication Critical patent/WO2019069866A1/fr
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to multi-component curable compositions.
  • Vehicles, aircraft and railways are being replaced by lightweight materials such as aluminum, magnesium, and carbon fiber composite materials other than steel as structural members for weight reduction, and multi-materialization in which multiple materials are used in one vehicle body It is increasing.
  • Adhesive bonding using an adhesive is attracting attention, as it may be difficult in spot welding and laser welding for joining dissimilar materials. Since a steel plate, an aluminum alloy, and a fiber reinforced composite material have different coefficients of linear expansion, the adhesive is required to have flexibility to follow thermal strain. For this reason, epoxy resins having high rigidity may be disadvantageous, and materials having high elastic modulus and flexibility are required as new structural adhesives.
  • Patent Document 1 a composition comprising a reactive silicon group-containing polyoxyalkylene having high strength at break and flexibility and an epoxy resin is known (Patent Document 1), but as an adhesive for structural members, the strength is There were times when it was not enough.
  • Patent Document 2 Combination with Reactive Silicon Group-Containing (Meth) Acrylic Acid Ester-Based Polymer
  • Patent Document 3 Combination with Epoxy Resin and Reactive Silicon-Group-Containing (Meth) Acrylic Acid Ester-Based Polymer
  • Patent Reference 4 it is not easy to obtain a cured product having high rigidity required as a structural adhesive and flexibility to follow thermal strain.
  • a multi-component curable composition comprising an agent A containing (D), an epoxy resin (C), and an agent B containing a silanol condensation catalyst (E), the polyoxyalkylene (A) and The weight ratio of the (meth) acrylate polymer (B) is 95: 5 to 50:50, and the total of the polyoxyalkylene (A) and the (meth) acrylate polymer (B): epoxy resin
  • the multi-component curable composition according to (1) wherein the weight ratio of the polyoxyalkylene (A) to the (meth) acrylate polymer (B) is 70:30 to 50:50, (3).
  • the weight ratio of the total of the polyoxyalkylene (A) and the (meth) acrylic acid ester-based polymer (B): the epoxy resin (C) is 80:20 to 60:40, as described in (1) or (2) Multi-component curable composition, (4).
  • the terminal site of the polyoxyalkylene (A) is represented by the general formula (1):
  • R 1 and R 3 are each independently a divalent linking group having 1 to 6 carbon atoms, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen, nitrogen
  • R 2 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms
  • n is an integer of 1 to 10
  • R 5 is each independently a hetero-containing group Is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may have Y.
  • Y is a hydroxyl group or a hydrolyzable group
  • a is any of 1, 2 and 3.
  • the (meth) acrylic acid ester polymer (B) contains a polymer containing alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group in an amount of 40% by weight or more in all monomers (1)
  • the (meth) acrylate polymer (B) contains an alkyl (meth) acrylate having an alkyl carbon number of 1 to 3 of 40% by weight or more in all monomers, and an alkyl carbon Any one of (1) to (9), which contains a polymer containing 40% by weight or more of alkyl (meth) acrylate having a number of 4 to 30 in all monomers, and which is obtained by blending the both.
  • (Meth) acrylic acid ester polymer (B) has an alkyl alkyl (meth) acrylate having 1 to 3 carbon atoms in an amount of 40% by weight or more in all monomers, and an alkyl carbon number of 4 to 30
  • the multi-component curable composition according to any one of (1) to (9), which comprises a polymer containing 40% by weight or more of an alkyl (meth) acrylate in all monomers, (13).
  • a structural adhesive comprising the multi-component curable composition according to any one of (1) to (14), (16).
  • a curable composition having high strength, high rigidity and flexibility after curing is obtained, and a cured product obtained by curing the composition.
  • This provides an adhesive useful as a structural adhesive.
  • the present invention comprises a polyoxyalkylene (A) having more than one reactive silicon group at one end, a reactive silicon group-containing (meth) acrylate polymer (B), and a tertiary amine A agent containing an epoxy resin curing agent (D), B agent containing epoxy resin (C) and silanol condensation catalyst (E), A multi-component curable composition comprising The weight ratio of the polyoxyalkylene (A) to the (meth) acrylic ester polymer (B) is 95: 5 to 50:50, and the polyoxyalkylene (A) to the (meth) acrylic ester polymer ( It is a multicomponent curable composition in which the weight ratio of the total of B): epoxy resin (C) is 90:10 to 50:50.
  • the curable composition having the above-mentioned constitution provides a cured product having high rigidity and flexibility.
  • polyoxyalkylene (A) having more than one reactive silicon group at one end
  • the polyoxyalkylene (A) also referred to as “polyoxyalkylene (A)” having more than one reactive silicon group at one end of the present invention has more than one reactive silicon group at one end.
  • polyoxyalkylene having more than one reactive silicon group at one end means that it has an average of more than one reactive silicon group at one end
  • polyoxyalkylene (A) It is shown that polyoxyalkylene containing two or more reactive silicon groups is contained at one terminal site. That is, polyoxyalkylene (A) may contain only polyoxyalkylene having two or more reactive silicon groups in one terminal site, or two or more reactions in one terminal site. It may contain both of the polyoxyalkylene containing a reactive silicon group and the polyoxyalkylene containing one reactive silicon group at one terminal site. In addition, there may be both an end containing two or more reactive silicon groups and an end containing one reactive silicon group at a plurality of ends possessed by one molecule of polyoxyalkylene. Furthermore, as long as polyoxyalkylene (A) has an average of more than one reactive silicon group at one end, the polyoxyalkylene (A) contains polyoxyalkylene containing a terminal site having no reactive silicon group. May be
  • end in the present invention includes the chain end and its neighboring structure in the polymer molecular chain. More specifically, it may be defined as a group to be substituted on the number of atoms corresponding to 20%, more preferably 10%, from the end of the bonding atoms constituting the polymer molecular chain. Also, in terms of the number of bonding atoms, the terminal site may be defined as the terminal site, up to 30 atoms from the end of the polymer molecular chain, more preferably up to 20 atoms.
  • the reactive silicon group of the polyoxyalkylene (A) may have an average of more than 1.0 at one end, but is preferably 1.1 or more, 1.5 or more Is more preferably 2.0, and more preferably 2.0 or more.
  • the upper limit is preferably 5 or less, more preferably 3 or less.
  • the number of terminal portions having one or more reactive silicon groups contained in one polyoxyalkylene (A) molecule is preferably 0.5 or more on average, and 1.0 or more on average. Some are more preferable, 1.1 or more is more preferable, and 1.5 or more is most preferable.
  • the upper limit is preferably 4 or less, more preferably 3 or less.
  • the polyoxyalkylene (A) may have a reactive silicon group in addition to the terminal site, but having a reactive silicon group only at the terminal site is a rubbery cured material exhibiting high elasticity and low elastic modulus. It is preferable because the product can be easily obtained.
  • the terminal structure of polyoxyalkylene (A) has the general formula (1):
  • R 1 and R 3 are each independently a divalent linking group having 1 to 6 carbon atoms, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen, nitrogen
  • R 2 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms
  • n is an integer of 1 to 10
  • R 5 is each independently a hetero-containing group Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may have Y.
  • Y is a hydroxyl group or a hydrolysable group
  • a is any one of 1, 2 and 3. It is preferable that R 1 in the general formula (1) be CH 2 OCH 2 and R 3 be CH 2 , and it is further preferable that R 2 and R 4 be hydrogen atoms.
  • R 1 may be a divalent organic group having 1 to 6 carbon atoms, and examples thereof include CH 2 OCH 2 , CH 2 O, and CH 2 , preferably CH 2 OCH 2 . .
  • R 2 and R 4 include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom.
  • R 3 for example, CH 2 and CH 2 CH 2 can be mentioned, and preferably CH 2 .
  • R 5 examples include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N, N-diethylaminomethyl group, preferably methyl group, ethyl group, chloromethyl group and methoxymethyl group. More preferably, it is a methyl group or a methoxymethyl group.
  • Examples of Y include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group.
  • an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.
  • Specific examples of the reactive silicon group (SiR 5 3-a Y a ) possessed by the polyoxyalkylene (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, and a triethylsilyl group.
  • Acetoxysilyl group dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) di Examples thereof include, but are not limited to, ethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group and the like.
  • a diethylaminomethyl) dimethoxysilyl group exhibits high activity, and a cured product having good mechanical properties is preferably obtained, and a cured product having a high Young's modulus can be obtained, so a trimethoxysilyl group and a triethoxysilyl group are more preferred.
  • main chain skeleton of polyoxyalkylene (A) there is no particular limitation on the main chain skeleton of polyoxyalkylene (A), and for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene -Polyoxybutylene copolymer etc. are mentioned. Among them, polyoxypropylene is preferred.
  • the number average molecular weight of the polyoxyalkylene (A) is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene equivalent in GPC. . If the number average molecular weight is less than 3,000, the amount of introduced reactive silicon groups will be large, which may be inconvenient in terms of manufacturing cost, and if it exceeds 100,000, the viscosity will be high, and the point of workability Tend to be inconvenient.
  • the method of measuring the hydroxyl value of JIS K 1557 and the method of measuring the iodine number specified in JIS K 0070 of the organic polymer precursor before introducing the reactive silicon group The terminal group concentration can be measured directly by titration analysis based on the principle, and the terminal group conversion molecular weight determined in consideration of the structure of the organic polymer (the degree of branching determined by the used polymerization initiator) can also be shown.
  • the terminal group conversion molecular weight of polyoxyalkylene (A) is obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned terminal group conversion molecular weight, and the polyoxyalkylene (A) It is also possible to determine the number average molecular weight determined by GPC and convert it to a terminal group equivalent molecular weight.
  • the molecular weight distribution (Mw / Mn) of the polyoxyalkylene (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, and still more preferably 1.5 or less. 4 or less is especially preferable.
  • the molecular weight distribution of polyoxyalkylene (A) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.
  • the reactive silicon group is localized at the terminal of the polyoxyalkylene (A) of the present invention
  • the main chain structure is preferably linear.
  • Polyoxyalkylene (A) is a reactive silicon group which reacts with a carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds at one end of a hydroxyl group-terminated polymer obtained by polymerization. Preferably, they are obtained by reacting the contained compounds.
  • the above preferable synthesis method is described below.
  • the polyoxyalkylene (A) is preferably a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex.
  • ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, polypropylene monoalkyl ether, etc. have one or more hydroxyl groups. The thing is mentioned.
  • Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.
  • alkali metal salt used in the present invention sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable.
  • Sodium methoxide is particularly preferred in view of availability.
  • As temperature at the time of making an alkali metal salt act 50 degreeC or more and 150 degrees C or less are preferable, and 110 degreeC or more and 140 degrees C or less are more preferable.
  • As time at the time of making an alkali metal salt act 10 minutes or more and 5 hours or less are preferable, and 30 minutes or more and 3 hours or less are more preferable.
  • the addition amount of the epoxy compound having a carbon-carbon unsaturated bond used in the present invention may be any amount in consideration of the introduction amount and reactivity of the carbon-carbon unsaturated bond to the polymer.
  • the lower limit of the molar ratio to the hydroxyl group contained in the polymer is preferably 0.2 or more, and more preferably 0.5 or more.
  • the upper limit is preferably 5.0 or less, more preferably 2.0 or less.
  • the reaction temperature for ring-opening addition reaction of an epoxy compound having a carbon-carbon unsaturated bond with a polymer containing a hydroxyl group is preferably 60 ° C. or more and 150 ° C. or less. More preferably, the temperature is 110 ° C. or more and 140 ° C. or less.
  • halogenated hydrocarbon compounds having a carbon-carbon unsaturated bond used in the present invention include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, iodide It is preferable to use allyl chloride or methallyl chloride for ease of handling.
  • the addition amount of the above-mentioned halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the lower limit of the molar ratio to the hydroxyl group contained in the polyoxyalkylene polymer is 0.7 or more. Is preferable, and 1.0 or more is more preferable.
  • the upper limit is preferably 5.0 or less, more preferably 2.0 or less.
  • the temperature for reacting the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferably 50 ° C. or more and 150 ° C. or less, and more preferably 110 ° C. or more and 140 ° C. or less.
  • the reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.
  • the method for introducing the reactive silicon group is not particularly limited, and known methods can be used.
  • the following shows an introduction method.
  • (I) A method in which a hydrosilane compound is added to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.
  • (Ii) A polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of reacting with the carbon-carbon unsaturated bond to form a bond and a reactive silicon group (also referred to as a silane coupling agent) How to react.
  • the group capable of reacting with the carbon-carbon unsaturated bond to form a bond includes, but is not limited to, a mercapto group.
  • the method (i) is preferable because the reaction is simple, adjustment of the introduction amount of the reactive silicon group, and the physical properties of the reactive silicon group-containing polyoxyalkylene polymer (A) obtained are stable.
  • the method (ii) has many reaction options, and it is easy and preferable to increase the reactive silicon group introduction rate.
  • hydrosilane compounds used in the method of (i) are exemplified. Trimethoxysilane, triethoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, ( Methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (N, N-diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane and the like.
  • the amount of the hydrosilane compound used is such that the molar ratio to the carbon-carbon unsaturated bond (mole number of hydrosilane / mole number of carbon-carbon unsaturated bond) in the precursor polymer is 0.05 to 10 It is preferable from the point of sex, and 0.3 to 2 is more preferable from the point of economy.
  • the hydrosilylation reaction is accelerated by various catalysts.
  • known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium and the like may be used.
  • Reactive silicon group-containing (meth) acrylic acid ester based polymer (B) As a (meth) acrylic acid ester type monomer constituting the main chain of a reactive silicon group-containing (meth) acrylic acid ester type polymer (B) (also referred to as “(meth) acrylic acid ester type polymer (B)”) Is not particularly limited, and various ones can be used.
  • monomer units other than the above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylol acrylamide and N-methylol methacrylamide; glycidyl acrylate and glycidyl methacrylate And monomers containing an epoxy group, monomers containing a nitrogen-containing group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate, and the like.
  • (meth) acrylate polymer (B) a polymer obtained by copolymerizing a (meth) acrylate monomer and a vinyl monomer copolymerizable therewith can also be used.
  • the vinyl monomer is not particularly limited.
  • styrene monomers such as styrene, vinyl toluene, ⁇ -methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid And dialkyl esters; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, Maleimide-based monomers such as maleimide and cyclohe
  • a copolymer comprising a styrene-based monomer and a (meth) acrylic acid-based monomer is preferable because of excellent physical properties, and an acrylic acid ester monomer and methacrylic acid.
  • a (meth) acrylic acid ester-based polymer composed of an acid ester monomer is more preferable, and an acrylic acid ester-based polymer composed of an acrylic acid ester monomer is particularly preferable.
  • the (meth) acrylate polymer (B) has a reactive silicon group represented by the general formula (3). -SiR 5 3-a Y a (3) (Wherein, R 5 , Y and a are as defined above)
  • R 5 include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group and an N, N-diethylaminomethyl group, and a methyl group and an ethyl group are preferable.
  • Examples of Y include a hydroxyl group, hydrogen, a halogen, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group.
  • an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.
  • Specific examples of the reactive silicon group (SiR 5 3-a Y a ) possessed by the (meth) acrylate polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, and a tris (2-propenyl group).
  • Oxy) silyl group triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group Examples thereof include, but are not limited to, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, and (N, N-diethylaminomethyl) diethoxysilyl group.
  • a diethylaminomethyl) dimethoxysilyl group exhibits high activity, and a cured product having good mechanical properties is preferably obtained, and a cured product having a high Young's modulus can be obtained, so a trimethoxysilyl group and a triethoxysilyl group are more preferred.
  • the reactive silicon group equivalent of the (meth) acrylate polymer (B) is not particularly limited, but 0.2 mmol / g or more is preferable, 0.5 mmol / g or more is more preferable, and 0.6 mmol / g or more Is more preferred. 2.0 mmol / g or less is preferable and, as for the upper limit of the said reactive silicon equivalent, 1.0 mmol / g or less is more preferable from the point which suppresses the fall of elongation of hardened
  • the method for introducing the reactive silicon group into the (meth) acrylate polymer is not particularly limited, and the following method can be used, for example.
  • (Iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group with the above-mentioned monomer. Using this method, reactive silicon groups tend to be randomly introduced into the polymer backbone.
  • (V) A method of polymerizing a (meth) acrylic acid ester polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. Using this method, reactive silicon groups can be introduced at the polymer end.
  • (Vi) A method in which a compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then a compound having a reactive silicon group and a functional group reactive to the V group is reacted. Specifically, after copolymerizing 2-hydroxyethyl acrylate, a method of reacting isocyanate silane having a reactive silicon-containing group, or after copolymerizing glycidyl acrylate, an aminosilane compound having a reactive silicon-containing group And the like.
  • (Vii) A method of modifying a terminal functional group of a (meth) acrylic acid ester-based polymer synthesized by a living radical polymerization method to introduce a reactive silicon group.
  • the (meth) acrylic acid ester-based polymer obtained by the living radical polymerization method can easily introduce a functional group at the polymer end, and by modifying this, a reactive silicon group can be introduced at the polymer end.
  • the compound having a polymerizable unsaturated group and a reactive silicon group used in the method (iv) is 3- (dimethoxymethylsilyl) propyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate , (Meth) acrylic acid 3- (triethoxysilyl) propyl, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid (trimethoxysilyl) methyl, (meth) acrylic acid (triethoxysilyl) methyl And 3-((methoxymethyl) dimethoxysilyl) propyl (meth) acrylate. From the viewpoint of availability, 3- (dimethoxymethylsilyl) propyl (meth) acrylate and 3- (trimethoxys
  • mercaptosilane compound having a reactive silicon-containing group used in the method (v) 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, (mercaptomethyl) trimethoxy Silane, etc. may be mentioned.
  • Examples of the compound having a reactive silicon group and a functional group reactive to a V group used in the method (vi) include 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, isocyanate Isocyanate silane compounds such as methyldimethoxymethylsilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane; 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Epoxysilane compounds such as silane, glycidoxymethyltrimethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyltriethoxysilane; 3- Minopropyldimethoxymethylsilane, 3-aminopropyltrime
  • any modification reaction can be used in the method of (vii) above, for example, a method using a compound having a functional group capable of reacting with a terminal reactive group obtained by polymerization and a silicon group, or a terminal reactive group and A double bond can be introduced at the polymer end using a compound having a functional group capable of reacting and a double bond, and a reactive silicon group can be introduced to this by hydrosilylation or the like.
  • the (meth) acrylic acid ester polymer (B) contains a polymer containing an alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group in an amount of 40% by weight or more based on all monomers.
  • a polymer that contains 40% by weight or more of an alkyl (meth) acrylate having 4 to 30 carbon atoms of alkyl in all monomers is preferable because it is rigid, and it is obtained by blending both. It is preferable to improve the rigidity, the elongation and the strength.
  • the (meth) acrylate polymer (B) has an alkyl (meth) acrylate having an alkyl carbon number of 1 to 3 in an amount of 40% by weight or more based on all monomers and an alkyl carbon number of 4 to It is also preferable to contain a polymer obtained by copolymerizing a monomer mixture containing 40% by weight or more of the alkyl (meth) acrylate, which is 30, in all monomers, since the rigidity, elongation and strength are improved.
  • the monomer composition of the (meth) acrylate polymer (B) can be selected according to the application and purpose. For applications requiring strength, those having a relatively high glass transition temperature (Tg) are preferable And 0 ° C. or more and 200 ° C. or less are preferable, and those having a Tg of 20 ° C. or more and 100 ° C. or less are more preferable. In addition, Tg is calculated
  • the number average molecular weight of the (meth) acrylate polymer (B) is not particularly limited, but is preferably 500 to 50,000, more preferably 500 to 30,000, in terms of polystyrene equivalent molecular weight by GPC measurement. -10,000 are particularly preferred.
  • the method of blending the (meth) acrylate polymer (B) and the polyoxyalkylene (A) is disclosed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, It is proposed by the publication 11-116763 gazette etc.
  • a method of polymerizing a (meth) acrylic acid ester monomer in the presence of a polyoxypropylene polymer having a reactive silicon group can be used.
  • the weight ratio (A) :( B) of polyoxyalkylene (A) to (meth) acrylate polymer (B) is 95: 5 to 50:50. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Furthermore, it is preferable that (A) :( B) is 70:30 to 50:50 in terms of achieving both high rigidity and flexibility.
  • Epoxy resin (C) is epichlorohydrin-bisphenol A epoxy resin, epichlorohydrin-bisphenol F epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac epoxy resin, hydrogenated bisphenol A epoxy resin Glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-hydroxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins Resin, N, N-diglycidyl aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as tellurium, glycerin
  • the amount of the epoxy resin (C) used is such that the ratio (A + B) of the total of the polyoxyalkylene (A) and the (meth) acrylic acid ester polymer (B) to the epoxy resin (C): (C) is 90: Use 10 to 50:50.
  • (A + B) is more than 90%, the strength is reduced, and when it is less than 50%, the flexibility is reduced and the film becomes too hard.
  • the ratio is 80:20 to 60:40 in terms of the balance between flexibility and strength.
  • Epoxy resin curing agent having tertiary amine (D) As a curing agent for curing the epoxy resin (C), an epoxy resin curing agent (D) having a tertiary amine is used. By using the epoxy resin curing agent (D) having a tertiary amine, a cured product having high rigidity, high strength and high elongation can be obtained.
  • any compound having a tertiary amine can be used.
  • the epoxy resin curing agent (D) having a tertiary amine is preferably an aromatic amine, and more preferably has three or more amino groups. Specifically, 2,4,6-tris (dimethylaminomethyl) phenol can be exemplified.
  • the amount of the epoxy resin curing agent (D) used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the epoxy resin (C), and 0 More preferably, it is from 5 to 10 parts by weight.
  • Silanol condensation catalyst (E) >> In the present invention, a silanol condensation catalyst is used to promote the reaction of condensing reactive silyl groups of polyoxyalkylene (A) and (meth) acrylic acid ester polymers (B) and to chain-extend or crosslink the polymers. Use (E).
  • silanol condensation catalyst (E) examples include organic tin compounds, metal salts of carboxylic acids, amine compounds, carboxylic acids, and alkoxy metals.
  • organic tin compound examples include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis (butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis (acetylacetonate), dioctyltin bis (acetylaceto) Neat), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reaction product of dibutyltin oxide and silicate compound, reaction product of dioctyltin oxide and silicate compound, dibutyltin oxide and phthalate ester The reaction products of
  • carboxylic acid metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, and the like.
  • carboxylic acid metal salt the following carboxylic acids and various metals can be combined.
  • amine compound examples include amines such as octylamine, 2-ethylhexylamine, laurylamine and stearylamine; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,1 Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo [4,3,0] nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, diphenylguanidine, etc .; butylbiguanide, 1-o-tolylbiguanide or 1- Biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine compounds and the like.
  • amines such as octylamine, 2-ethylhexylamine, laurylamine and stearylamine
  • DBU 1,8-diazabicyclo [5,4,0] undecene-7
  • DBN 1,1 Nitrogen-containing
  • carboxylic acid examples include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid and the like.
  • alkoxy metal examples include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), diisopropoxyaluminum ethyl acetoacetate And aluminum compounds, and zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), diisopropoxyaluminum ethyl acetoacetate And aluminum compounds
  • zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • the amount of the silanol condensation catalyst (E) used is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene (A) and the (meth) acrylate polymer (B), Furthermore, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable.
  • Water (F) may be added to the agent B of the composition of the present invention.
  • the addition of water accelerates the curing of the polyoxyalkylene (A) and the (meth) acrylate polymer (B) when the agent A and the agent B are mixed.
  • the amount of water (F) added is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene (A) and the (meth) acrylic acid ester polymer (B). -5 parts by weight is more preferable, and 0.1-2 parts by weight is more preferable.
  • composition of the present invention may contain, in addition to agents A and B, agent C containing water (F).
  • agent C containing water
  • the composition of the present invention is a three-pack type.
  • the composition of the present invention includes polyoxyalkylene (A), (meth) acrylate polymer (B), epoxy resin (C), epoxy resin curing agent (D), silanol condensation catalyst (E), water
  • fillers, adhesiveness imparting agents, anti-sagging agents, antioxidants, light stabilizers, ultraviolet light absorbers, tackifying resins, and other resins may be added as additives.
  • additives include, for example, plasticizers, solvents, diluents, photocurable substances, oxygen curable substances, surface property modifiers, silicates, hardenability modifiers, radical inhibitors, metal inactivation Agents, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, fungicides, flame retardants, blowing agents and the like.
  • fillers can be incorporated into the composition of the present invention.
  • fillers heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silica, hydrated silica, Carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, filaments and the like can be mentioned.
  • the amount of the filler used is preferably 1 to 300 parts by weight, particularly 10 to 250 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene (A) and the (meth) acrylate polymer (B). preferable.
  • An organic balloon and an inorganic balloon may be added for the purpose of weight reduction (reduction in specific gravity) of the composition.
  • Adhesive agent An adhesion promoter can be added to the composition of the present invention.
  • a silane coupling agent and a reaction product of a silane coupling agent can be added.
  • silane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, etc .; ⁇ -isocyanate propyltrimethoxysilane, ⁇ -isocyanate propyl tri Isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyanatomethyldime
  • the adhesion promoter may be used alone or in combination of two or more. Also, reactants of various silane coupling agents can be used.
  • the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene (A) and the (meth) acrylic acid ester polymer (B), and particularly preferably 0. 5 to 10 parts by weight is preferred.
  • an anti-sagging agent may be added, if necessary, in order to prevent the sagging and to improve the workability.
  • the anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
  • the use amount of the anti-sagging agent is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene (A) and the (meth) acrylic acid ester polymer (B).
  • An antioxidant can be used in the composition of the present invention.
  • the use of an antioxidant can improve the weatherability of the cured product.
  • examples of the antioxidant include hindered phenols, monophenols, bisphenols and polyphenols. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly 0.2 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene (A) and the (meth) acrylate polymer (B). -5 parts by weight are preferred.
  • Light stabilizers can be used in the compositions of the present invention.
  • the use of a light stabilizer can prevent the photooxidative deterioration of the cured product.
  • benzotriazole type, hindered amine type, benzoate type compounds and the like can be exemplified, but particularly hindered amine type is preferable.
  • the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly 0.2 parts by weight, based on 100 parts by weight of the total of polyoxyalkylene (A) and (meth) acrylic acid ester polymer (B). -5 parts by weight are preferred.
  • UV absorbers can be used in the compositions of the present invention.
  • the use of a UV absorber can enhance the surface weatherability of the cured product.
  • UV absorbers include benzophenone type, benzotriazol type, salicylate type, substituted tolyl type and metal chelate type compounds.
  • benzotriazole type is preferable, and the commercial names tinuvin P, tinuvin 213, tinuvin 234, tinuvin 326, There may be mentioned Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (all from BASF).
  • the amount of the UV absorber used is preferably 0.1 to 10 parts by weight, particularly 0.2 parts by weight, based on 100 parts by weight of the total of polyoxyalkylene (A) and (meth) acrylic acid ester polymer (B). -5 parts by weight are preferred.
  • a tackifier resin can be added for the purpose of enhancing the adhesion to the substrate and the adhesion, or as needed.
  • the tackifying resin is not particularly limited, and those generally used can be used.
  • terpene resins aromatically modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone indene resins, rosin resins Resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, styrene block copolymer and hydrogenated product thereof, petroleum resin (for example, C5 hydrocarbon resin, C9 Hydrocarbon resin, C5C9 hydrocarbon copolymer resin etc.), hydrogenated petroleum resin, DCPD resin etc. are mentioned. These may be used alone or in combination of two or more.
  • the amount of tackifier resin used is preferably 2 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene (A) and the (meth) acrylate polymer (B). Is more preferable, and 5 to 30 parts by weight is even more preferable. If the amount is less than 2 parts by weight, adhesion to the substrate and the adhesion effect are difficult to obtain, and if it exceeds 100 parts by weight, the viscosity of the composition may be too high and handling may be difficult.
  • the curable composition of the present invention comprises, as an agent A, a polyoxyalkylene (A), an acrylic ester polymer (B), an epoxy curing agent having a tertiary amine (D), and other additives. It is preferable to prepare an epoxy resin (C), a silanol condensation catalyst (E), and other additives as the B agent, and to prepare the A agent and the B agent as a two-component type before mixing. Furthermore, water may be added to the agent B in order to accelerate the curability of the polyoxyalkylene (A) and the acrylic ester polymer (B).
  • the composition of the present invention is suitable for use as an adhesive composition, and can be used for sealing materials for buildings, ships, vehicles, roads, etc., adhesives, adhesives, waterproofing materials, and the like.
  • the cured product obtained by curing the curable composition of the present invention has flexibility despite the excellent high rigidity, and among the uses described above, it can be used more as an adhesive, particularly as a structural adhesive.
  • Applications used include adhesives used in automotive parts such as vehicle panels, large vehicle parts such as trucks and buses, parts for train vehicles, aircraft parts, marine parts, electrical parts, various mechanical parts, etc. Is preferred.
  • the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
  • Liquid delivery system Tosoh HLC-8120 GPC Column: Tosoh TSK-GEL H type solvent: THF Molecular weight: converted to polystyrene Measurement temperature: 40 ° C
  • the hydroxyl value is determined by the measurement method of JIS K 1557
  • the iodine value is determined by the measurement method of JIS K 0070
  • the structure of the organic polymer (degree of branching determined by the used polymerization initiator) It is a molecular weight determined by taking into consideration.
  • the average number of carbon-carbon unsaturated bonds introduced into one terminal of the polymer (Q) shown in the examples was calculated by the following formula.
  • (Average number of introductions) [Unsaturated group concentration (mol / g) of polymer (Q) determined from iodine value--Unsaturated group concentration of precursor polymer (P) determined from iodine value (mol / g)] / [Hydroxyl concentration (mol / g) of precursor polymer (P) determined from hydroxyl value].
  • the average introduction number of silyl groups per one terminal of the polymer (A) shown in the examples was calculated by NMR measurement.
  • composition example 3 Polymerization in a mixture of 300 g methyl methacrylate, 115 g 2-ethylhexyl acrylate, 46 g ⁇ -methacryloxypropyltrimethoxysilane, 37 g ⁇ -mercaptopropyltrimethoxysilane, and 140 g IBA in 200 g isobutyl alcohol (IBA) heated to 105 ° C. A solution of 11.5 g of azobis-2-methylbutyronitrile as an initiator was added dropwise over 5 hours.
  • IBA isobutyl alcohol
  • Example 1 The solid content of the reactive silyl group-containing polyoxypropylene (A-1) obtained in Synthesis Example 1 is 42 parts by weight and the methacrylic acid ester copolymer (B-1) obtained in Synthesis Example 3 is 28 parts by weight After mixing to give IBA, the IBA was removed by heating. The resulting mixture was mixed with 4 parts by weight of Ancamine K 54 (2,4,6-tris (dimethylaminomethyl) phenol Air Products Co., Ltd.) as an epoxy resin curing agent (D), and KBM-603 (N-) as a silane coupling agent.
  • Ancamine K 54 (2,4,6-tris (dimethylaminomethyl) phenol Air Products Co., Ltd.)
  • D epoxy resin curing agent
  • KBM-603 N-
  • the agent A and the agent B were mixed to form a sheet having a thickness of about 2 mm, followed by curing for 3 days under 23 ° C. and 50% RH conditions and 4 days under 50 ° C. conditions.
  • the sheet was punched into No. 3 dumbbell shape, and a tensile strength test was conducted at 23 ° C. and 50% RH to measure 50% elongation stress (M50), strength at break (TB), elongation at break (EB), and Young's modulus .
  • M50 50% elongation stress
  • TB strength at break
  • EB elongation at break
  • Young's modulus Young's modulus
  • the tensile strength was measured at a tensile speed of 200 mm / min using Shimadzu Autograph (AGS-J). The results are shown in Table 2.
  • Example 2-3 Comparative Example 1-28
  • Example 2-3 Comparative Example 1-28
  • Table 2 results are shown in Table 2.
  • "-" means unmeasured.
  • Example 1 in which (A) :( B) is 70:30 to 50:50 has a high Young's modulus and a high rigidity.
  • Comparative Examples 4 to 6 are comparative examples to be compared with Example 1.
  • Example 4 Comparative Example 8-11
  • Example 4 A composition was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3, and the dumbbell tensile properties were evaluated. The results are shown in Table 3.
  • Example 4 using the epoxy resin curing agent (D) having a tertiary amine has higher strength, higher elongation, and higher rigidity than Comparative Examples 8 to 11 not used.
  • Tables 2 and 3 compositions containing both a polyoxyalkylene (A) having more than one reactive silicon group at one end and an epoxy resin curing agent (D) having a tertiary amine, It can be seen that the composition containing only one of them has high strength, high elongation and high rigidity.
  • Example 5-11 A composition was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 4, and the dumbbell tensile properties were evaluated. The results are shown in Table 4.
  • Examples 5 to 11 have high strength and high elongation, and the reactive silicon group equivalent of the (meth) acrylic acid ester polymer (B) is 0.6 mmol / g or more and 1 mmol / g or less.
  • And 8 have high rigidity compared to Examples 6 and 7 in which the reactive silicon group equivalent is less than 0.6 mmol / g.
  • a polymer containing alkyl (meth) acrylate having 1 to 3 carbon atoms of alkyl (meth) acrylate in an amount of 40% by weight or more based on all monomers is used.
  • the rigidity is also high as compared with Examples 9 to 11 in which a polymer in which the amount of the alkyl (meth) acrylate used is less than 40% by weight to 3 is used. Further, alkyl (meth) acrylate having 1 to 3 carbon atoms of alkyl is 40% by weight or more in all monomers, and alkyl (meth) acrylate having 4 to 30 carbon atoms of alkyl is all monomers Example 8 using a (meth) acrylic ester polymer (B), which contains a polymer obtained by copolymerizing a monomer mixture containing 40% by weight or more of the alkyl carbon atoms, In addition to high rigidity, all points of high strength and flexibility as compared with Example 5 using a polymer having 40% by weight or less of alkyl (meth) acrylate having 4 to 30 in all monomers. Is excellent.
  • Example 12-13 The dumbbell tensile properties were evaluated in the same manner as in Example 1 except that the formulation shown in Table 5 was changed and the curing conditions of the sheet were changed to 7 days under conditions of 80 ° C. and 30 min and 23 ° C. The results are shown in Table 5.
  • the (meth) acrylic acid ester polymer (B) contains a polymer (B-1) containing 40% by weight or more of alkyl (meth) acrylate having 1 to 3 carbon atoms in alkyl in all monomers. Containing a polymer (B-6) containing at least 40% by weight of alkyl (meth) acrylate with 4 to 30 carbon atoms of alkyl in all monomers, and containing both The strength, the elongation, and the rigidity are improved as compared with the example 12 in which only the (B-1) is used.

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Abstract

L'invention fournit une composition durcissable présentant un objet durci après durcissement très résistant, très rigide et souple, et l'objet durci obtenu par durcissement de cette composition. Plus précisément, l'invention concerne une composition durcissable de type à plusieurs liquides qui contient un agent [A] et un agent [B], lequel agent [A] contient un polyoxyalkylène (A) ayant plus d'un groupes silicium réactifs à une extrémité, un polymère (B) à base d'ester d'acide (méth)acrylique comprenant un groupe silicium réactif, et un agent de durcissement de résine époxy (D) possédant une amine tertiaire, et lequel agent [B] contient une résine époxy (C) et un catalyseur de condensation de silanol (E). Le rapport massique du polyoxyalkylène (A) et du polymère (B) à base d'ester d'acide (méth)acrylique est compris entre ９５：５ et ５０：５０, et le rapport massique du total des composants (A) et (B) avec la résine époxy (C) est compris entre ９０：１０ et ５０：５０.
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US12221563B2 (en) 2019-08-06 2025-02-11 Kaneka Corporation Curable composition
JP7617843B2 (ja) 2019-08-06 2025-01-20 株式会社カネカ 硬化性組成物
WO2021024817A1 (fr) * 2019-08-06 2021-02-11 株式会社カネカ Composition durcissable
JP7341780B2 (ja) 2019-08-06 2023-09-11 株式会社カネカ 硬化性組成物
CN114207017A (zh) * 2019-08-06 2022-03-18 株式会社钟化 固化性组合物
JP7542548B2 (ja) 2019-09-25 2024-08-30 株式会社カネカ 硬化性組成物
JPWO2021059972A1 (fr) * 2019-09-25 2021-04-01
WO2021059972A1 (fr) * 2019-09-25 2021-04-01 株式会社カネカ Composition durcissable
JPWO2022009933A1 (fr) * 2020-07-10 2022-01-13
WO2022009933A1 (fr) * 2020-07-10 2022-01-13 株式会社カネカ Copolymère à base d'ester d'acide (méth)acrylique et composition durcissable à base de celui-ci
JP7736690B2 (ja) 2020-07-10 2025-09-09 株式会社カネカ （メタ）アクリル酸エステル系共重合体及びその硬化性組成物
CN114316137A (zh) * 2020-10-09 2022-04-12 罗门哈斯电子材料有限责任公司 高折射率材料
WO2023013487A1 (fr) * 2021-08-05 2023-02-09 株式会社カネカ Composition durcissable multicomposant et son utilisation

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