WO2023132323A1 - 硬化性組成物及びその硬化物 - Google Patents

硬化性組成物及びその硬化物 Download PDF

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WO2023132323A1
WO2023132323A1 PCT/JP2022/048595 JP2022048595W WO2023132323A1 WO 2023132323 A1 WO2023132323 A1 WO 2023132323A1 JP 2022048595 W JP2022048595 W JP 2022048595W WO 2023132323 A1 WO2023132323 A1 WO 2023132323A1
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聖 宮藤
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • 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

Definitions

  • the present invention relates to a curable composition containing a polymer having a reactive silicon group and a cured product thereof.
  • An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon group capable of forming a siloxane bond by a hydrolysis/condensation reaction (hereinafter also referred to as a "reactive silicon group”) can be used even at room temperature. Reacts with moisture, etc. It is known that a rubber-like cured product can be obtained by cross-linking such an organic polymer through a siloxane condensation reaction of reactive silicon groups.
  • the polyoxyalkylene polymer having a reactive silicon group has a relatively low viscosity, so it is excellent in workability when preparing or using a blended composition.
  • the resulting cured product has a good balance of performance such as mechanical properties, weather resistance, and dynamic durability, it is widely used for applications such as sealants, adhesives, and paints (see Patent Document 1).
  • Patent Document 3 for the purpose of eliminating the drawback that the curing speed of one-component moisture-curable adhesives using modified silicone or acrylic-modified silicone is slow, a curing agent having a high curing speed and excellent adhesiveness is disclosed.
  • Group-containing graft copolymers are described.
  • an adhesive containing an organic polymer having a reactive silicon group develops the desired adhesive strength by performing a long curing and curing process for several days after bonding adherends.
  • an adhesive containing an organic polymer having a reactive silicon group develops the desired adhesive strength by performing a long curing and curing process for several days after bonding adherends.
  • it is required to develop a certain level of adhesive strength in a relatively short period of time after bonding the adherends there are cases where it is required to develop a certain level of adhesive strength in a relatively short period of time after bonding the adherends.
  • the present invention provides a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer, wherein a relatively high
  • An object of the present invention is to provide a curable composition capable of exhibiting adhesive strength.
  • the present inventors have made intensive studies to solve the above problems, and found that a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer , by adopting a specific multi-liquid structure and using a specific monomer and chain transfer agent in the reactive silicon group-containing (meth)acrylic acid ester polymer, it was found that the above problems can be solved. , completed the present invention.
  • the present invention is a multi-component curable composition containing agent A and agent B
  • Agent A contains a polyoxyalkylene polymer (A) having a reactive silicon group, and a (meth)acrylic acid ester copolymer (B) having a reactive silicon group
  • Agent B contains at least one compound selected from the group consisting of a polyoxyalkylene polymer (A) having a reactive silicon group, a plasticizer (C), and an epoxy resin (D)
  • the monomer component constituting the (meth)acrylic acid ester copolymer (B) is (meth) acrylic acid ester (b1), A polymer (b2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (b3) having a mercapto group
  • the monomer component further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (b3) having a mercapto group is a reactive
  • R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms
  • X represents a hydroxyl group or a hydrolyzable group
  • a is 2 or 3.
  • the present invention also relates to a cured product obtained by curing the multicomponent curable composition.
  • a curable composition comprising a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer, wherein relatively high adhesive strength can be achieved in a short time.
  • a curable composition that can be developed can be provided.
  • Agent A contains at least a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylate copolymer (B) having a reactive silicon group.
  • Agent B contains at least one compound selected from the group consisting of (A) a polyoxyalkylene polymer having a reactive silicon group, (C) a plasticizer, and (D) an epoxy resin.
  • a polyoxyalkylene polymer (A) having a reactive silicon group (hereinafter also simply referred to as "polyoxyalkylene polymer (A)") is blended in agent A.
  • the polyoxyalkylene-based polymer (A) may be blended only with the A agent, or may be blended with the B agent in addition to the A agent.
  • the polyoxyalkylene polymer (A) has a reactive silicon group represented by the following general formula (1). —SiR 1 3-a X a (1) (Wherein, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a represents 2 or 3.)
  • the number of carbon atoms in the hydrocarbon group of R 1 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
  • Specific examples of R 1 include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group. Preferred are methyl group, ethyl group, chloromethyl group and methoxymethyl group, and more preferred are methyl group and methoxymethyl group.
  • Examples of X include halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group.
  • an alkoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable, since they are moderately hydrolyzable and easy to handle.
  • Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and dimethoxymethyl silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N ,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto.
  • methyldimethoxysilyl trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- Diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with high rigidity can be obtained. A trimethoxysilyl group is more preferred.
  • the polyoxyalkylene polymer (A) may have an average of 1 or less reactive silicon groups at one terminal site, or an average of more than 1 reactive silicon group at one terminal site may have a silicon group.
  • having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) has two or more reactive silicon groups at one terminal site. It shows that polyoxyalkylene is included.
  • a terminal site having two or more reactive silicon groups can be represented, for example, by the following general formula (2).
  • R 2 and R 4 each independently represent a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R 2 and R 4 are carbon, oxygen, nitrogen
  • Each of R 3 and R 5 independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10.
  • R 1 , X, and a represent the above formula (1) is as described above.
  • R 2 and R 4 may be a divalent organic group having 1 to 6 carbon atoms, or may be a hydrocarbon group which may contain an oxygen atom.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-4, more preferably 1-3, even more preferably 1-2.
  • Specific examples of R 2 include -CH 2 OCH 2 -, -CH 2 O- and -CH 2 -, preferably -CH 2 OCH 2 -.
  • R 4 include -CH 2 - and -CH 2 CH 2 -, preferably -CH 2 -.
  • the number of carbon atoms in the hydrocarbon groups of R 3 and R 5 is preferably 1-5, more preferably 1-3, even more preferably 1-2.
  • Specific examples of R 3 and R 5 include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom and a methyl group, more preferably a hydrogen atom.
  • the terminal portion represented by the general formula (2) is such that R 2 is —CH 2 OCH 2 —, R 4 is —CH 2 —, and R 3 and R 5 are each hydrogen atoms.
  • n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • n is not limited to one value, and may be a mixture of multiple values.
  • the polyoxyalkylene polymer (A) may have an average of 1.0 or less reactive silicon groups at one terminal site.
  • the average number is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more.
  • the polyoxyalkylene polymer (A) may have an average of more than 1.0 reactive silicon groups at one terminal site.
  • the average number is more preferably 1.1 or more, still more preferably 1.5 or more, and even more preferably 2.0 or more.
  • the average number is preferably 5 or less, more preferably 3 or less.
  • the polyoxyalkylene-based polymer (A) may have reactive silicon groups in addition to the terminal sites, but having them only at the terminal sites yields a rubber-like cured product with high elongation and low elastic modulus. It is preferable because it becomes easy to be
  • the average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, from the viewpoint of the strength of the cured product. , is more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more.
  • the average number may be 2.0 or less, or may be more than 2.0. From the viewpoint of elongation of the cured product, the number is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.
  • the main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, Examples include polyoxypropylene-polyoxybutylene copolymers. Among them, polyoxypropylene is preferred.
  • the main chain structure of the polyoxyalkylene polymer (A) may be linear or branched.
  • the main chain structure of the polyoxyalkylene polymer (A) is preferably branched because the initial adhesive strength is higher.
  • the branched main chain structure can be formed by polymerizing an epoxy compound in the presence of an initiator having 3 or more hydroxyl groups in one molecule.
  • the number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, in terms of polystyrene equivalent molecular weight in GPC, and particularly preferably It is 3,000 or more and 30,000 or less.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A) is not particularly limited, it is preferably narrow, specifically less than 2.0, more preferably 1.6 or less. 5 or less is more preferable, and 1.4 or less is particularly preferable. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less.
  • the molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the method for synthesizing the polyoxyalkylene polymer (A) is not particularly limited.
  • an initiator having a hydroxyl group is polymerized with an epoxy compound to obtain a hydroxyl group-terminated polymer.
  • an alkali metal salt for example, sodium methoxide
  • a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond for example, allyl chloride
  • a reactive silicon group-containing polyoxyalkylene polymer (A) can be obtained by reacting with a reactive silicon group-containing hydrosilane compound (eg, dimethoxymethylsilane, trimethoxysilane).
  • a polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site which is a preferred embodiment, can be obtained as follows. After reacting the hydroxyl group of the hydroxyl-terminated polymer with the alkali metal salt in the same manner as described above, an epoxy compound having a carbon-carbon unsaturated bond (eg, allyl glycidyl ether) is first reacted, and then the carbon-carbon unsaturated bond is reacted. Two or more carbon-carbon unsaturated bonds are introduced at one end by reacting a halogenated hydrocarbon compound having a saturated bond (eg, allyl chloride). After that, a reactive silicon group-containing hydrosilane compound may be reacted.
  • an epoxy compound having a carbon-carbon unsaturated bond eg, allyl glycidyl ether
  • Two or more carbon-carbon unsaturated bonds are introduced at one end by reacting a halogenated hydrocarbon compound having a saturated bond (eg,
  • a cured product obtained from a curable composition containing a polyoxyalkylene polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds and the like.
  • the polyoxyalkylene polymer (A) containing amide segments and the like may be cleaved by heat or the like.
  • a curable composition containing a polyoxyalkylene polymer (A) containing an amide segment or the like tends to have a high viscosity.
  • polyoxyalkylene polymer (A) a polyoxyalkylene containing an amide segment or the like may be used, or a polyoxyalkylene containing no amide segment or the like may be used. You may
  • Examples of the amide segment represented by the general formula (3) include the reaction between an isocyanate group and a hydroxyl group, the reaction between an amino group and a carbonate, the reaction between an isocyanate group and an amino group, and the reaction between an isocyanate group and a mercapto group. and the like.
  • the amide segment represented by the general formula (3) also includes those formed by the reaction of the amide segment containing an active hydrogen atom with an isocyanate group.
  • a polyoxyalkylene having an active hydrogen-containing group at its terminal is reacted with a polyisocyanate compound to produce a polymer having an isocyanate group at its terminal.
  • a compound having both a functional group for example, a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group
  • a method of reacting is mentioned.
  • Another example is a method of reacting a polyoxyalkylene having an active hydrogen-containing group at its end with a reactive silicon group-containing isocyanate compound.
  • the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, and 1.5 to 5. is more preferred, and 2 to 3 are particularly preferred. If this number is less than 1, the curability may not be sufficient, and conversely if it is greater than 10, the polyoxyalkylene polymer (A) may become highly viscous and difficult to handle. There is In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (A) preferably does not contain an amide segment.
  • Agent A includes a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic acid ester copolymer (B) having a reactive silicon group (hereinafter simply referred to as "(meth)acrylic acid Also referred to as "ester-based copolymer (B)").
  • the (meth)acrylic ester-based copolymer (B) may be blended only in the A agent, or may be blended in each of the A agent and the B agent.
  • the (meth)acrylic acid ester-based copolymer (B) has a reactive silicon group represented by the above formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
  • the reactive silicon group of the (meth)acrylate copolymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene polymer (A).
  • Specific examples of the reactive silicon group possessed by the (meth)acrylate copolymer (B) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group.
  • dimethoxymethylsilyl group diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like.
  • methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- Diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with a high Young's modulus is obtained. , and a trimethoxysilyl group are more preferred.
  • the reactive silicon group equivalent of the (meth)acrylate copolymer (B) is not particularly limited, but is preferably 0.2 mmol/g or more, more preferably 0.5 mmol/g or more, and 0.6 mmol/g. The above is more preferable.
  • the reactive silicon group equivalent is preferably 2.0 mmol/g or less, and more preferably 1.0 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product.
  • the reactive silicon group equivalent is particularly preferably 0.5 mmol/g or more and 1.0 mmol/g or less.
  • the (meth)acrylic acid ester-based copolymer (B) includes at least a (meth)acrylic acid ester (b1), a polymer (b2) having more than one (meth)acryloyl group in the molecule, and a mercapto It is a polymer formed by copolymerizing a monomer component containing a chain transfer agent (b3) having a group.
  • “(meth)acryl” means "acryl and/or methacryl”.
  • the (meth)acrylic acid ester-based copolymer (B) has reactive silicon groups by satisfying either one or both of the following two conditions.
  • Condition 1 The monomer component further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group.
  • Condition 2 The chain transfer agent (b3) having a mercapto group further has a reactive silicon group.
  • the number of reactive silicon groups introduced under Condition 2 is greater than the number of reactive silicon groups introduced under Condition 1.
  • the reactive silicon group equivalent introduced under Condition 1 is preferably 0.01 mmol/g or more, more preferably 0.03 mmol/g or more, and even more preferably 0.05 mmol/g or more.
  • the reactive silicon group equivalent introduced under Condition 1 is preferably 1.0 mmol/g or less, more preferably 0.5 mmol/g or less.
  • the reactive silicon group equivalent introduced under Condition 2 is preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more, and even more preferably 0.5 mmol/g or more.
  • the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
  • the reactive silicon group equivalent introduced under Condition 1 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. Further, the reactive silicon group equivalent introduced under Condition 1 is preferably 1.8 mmol/g or less, more preferably 1.0 mmol/g or less.
  • the reactive silicon group equivalent introduced under Condition 2 is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.3 mmol/g or more. In addition, the reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less.
  • the (meth)acrylic acid ester (b1) is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) ) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) ) n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate,
  • the content of the (meth)acrylic acid ester (b1) is 30% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (B). It is preferably at least 40% by weight, even more preferably at least 45% by weight.
  • the upper limit is preferably 80% by weight or less, more preferably 70% by weight or less, and even more preferably 65% by weight or less.
  • the (meth)acrylic acid ester (b1) preferably contains a (meth)acrylic acid alkyl ester in which the alkyl has 1 to 4 carbon atoms, since a cured product with high strength can be obtained.
  • the (meth)acrylic acid alkyl ester in which the alkyl has 1 to 4 carbon atoms is contained in an amount of 30% by weight or more based on the total amount of the monomer components constituting the (meth)acrylic acid ester-based copolymer (B). 35% by weight or more is more preferable, and 40% by weight or more is even more preferable.
  • the upper limit is preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 55% by weight or less.
  • (Meth)acrylic acid ester (b1) can form a hard polymer chain to obtain a cured product with high strength. It preferably contains at least one monomer selected from the group consisting of dicyclopentanyl. In particular, among the total amount of the monomer components excluding the polymer (b2), at least one selected from the group consisting of methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate The proportion of the seed monomer is preferably 60% by weight or more, more preferably 70% by weight or more.
  • Polymer (b2) having more than one (meth)acryloyl group in the molecule is itself a polymer, it is one of the monomers constituting the (meth)acrylate copolymer (B). Since the polymer (b2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (b1). Moreover, since the polymer (b2) has more than one (meth)acryloyl group in one molecule, it can function as a so-called polyfunctional macromonomer.
  • the main chain skeleton (second molecular chain described later) of the polymer (b2) is mainly composed of the (meth)acrylic acid ester (b1) in the (meth)acrylic acid ester-based copolymer (B) 2 It can form a structure that crosslinks the molecular chains (the first molecular chain described later).
  • the polymer (b2) is also referred to as polyfunctional macromonomer (b2).
  • the (meth)acryloyl group of the polyfunctional macromonomer (b2) is preferably represented by the following formula (4).
  • CH2 C( R7 )-COO-Z (4)
  • R 7 represents hydrogen or a methyl group.
  • Z represents the main chain skeleton of the polyfunctional macromonomer (b2).
  • the polyfunctional macromonomer (b2) has an average of more than one (meth)acryloyl group in one molecule.
  • the average number of (meth)acryloyl groups per molecule of the polyfunctional macromonomer (b2) is preferably 1.1-5, more preferably 1.3-4, and 1.6-2. 5 is more preferred, and 1.8 to 2.0 is particularly preferred.
  • the polyfunctional macromonomer (b2) may have only an acryloyl group, may have only a methacryloyl group, or may have both an acryloyl group and a methacryloyl group. You may
  • the polyfunctional macromonomer (b2) can have (meth)acryloyl groups at either or both of the molecular chain terminals and side chains of the polymer. From the standpoint of excellent mechanical properties, it is preferred to have it at the end of the molecular chain. In particular, it is particularly preferred that the polyfunctional macromonomer (b2) has a linear main chain skeleton and (meth)acryloyl groups at both ends of the molecular chain.
  • the main chain skeleton of the polyfunctional macromonomer (b2) is preferably a (meth)acrylate polymer or a polyoxyalkylene polymer.
  • the polyfunctional macromonomer (b2) whose main chain skeleton is a (meth)acrylic acid ester polymer is denoted as (b2′), and the main chain skeleton is a polyoxyalkylene polymer.
  • Macromonomer (b2) is denoted as (b2′′).
  • the monomer constituting the main chain skeleton of the polyfunctional macromonomer (b2') is not particularly limited, and various (meth)acrylic monomers can be used.
  • (meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( meth) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( meth)n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)
  • monomers that are copolymerizable with the (meth)acrylic monomer may be used in combination.
  • Other monomers include, for example, styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Monomer; Maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, and maleic acid dialkyl ester; Fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl ester, and fumaric acid dialkyl ester; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, o
  • the main chain skeleton of the polyfunctional macromonomer (b2') is preferably composed of a soft polymer.
  • the monomer component forming the main chain skeleton of the polyfunctional macromonomer (b2′) is an acrylate ester (provided that isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentaacrylate excluding nil) is preferably 60% by weight or more, more preferably 70% by weight or more. The upper limit may be 100% by weight.
  • the method for synthesizing the polyfunctional macromonomer (b2') is not particularly limited, for example, the method shown below can be used. The following methods may be used in combination.
  • a copolymer obtained by copolymerizing a monomer having a reactive functional group (V group) e.g., acrylic acid, 2-hydroxyethyl acrylate
  • V group e.g., acrylic acid, 2-hydroxyethyl acrylate
  • a compound having a functional group and (meth)acryloyl group that reacts with group V eg, 2-isocyanatoethyl (meth)acrylate.
  • (ii) A method of polymerizing a (meth)acrylic monomer by a living radical polymerization method and then introducing (meth)acryloyl groups to the ends of the molecular chain (preferably both ends of the molecular chain).
  • a living radical polymerization method uses a cobalt porphyrin complex as shown, for example, in J. Am. Chem. Soc., 1994, 116, 7943.
  • Atom Transfer Radical Polymerization using a transition metal complex as a catalyst, and the like. Atom transfer radical polymerization is most preferred because it facilitates the introduction of (meth)acryloyl groups to the ends of the molecular chains.
  • the polyoxyalkylene polymer that is the main chain skeleton of the polyfunctional macromonomer (b2′′) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, and polyoxyethylene. -polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Among them, polyoxypropylene is preferred.
  • the main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but is preferably linear.
  • the method for synthesizing the polyfunctional macromonomer (b2′′) is not particularly limited, for example, a polyoxyalkylene polymer having more than one hydroxyl group in the molecule (preferably, a linear A method of preparing a polyoxyalkylene-based polymer) and introducing a (meth)acryloyl group using the hydroxyl group.
  • a polyoxyalkylene polymer having a hydroxyl group is reacted with a compound having an isocyanate group and a (meth)acryloyl group to form a urethane bond.
  • a compound having an isocyanate group and a (meth)acryloyl group can introduce a (meth)acryloyl group.
  • Specific examples of the compound having an isocyanate group and a (meth)acryloyl group include isocyanatoethyl (meth)acrylate, isocyanatopropyl (meth)acrylate, isocyanatobutyl (meth)acrylate, isocyanatohexyl (meth)acrylate, and the like. be done.
  • a polyoxyalkylene polymer having a hydroxyl group is reacted with a diisocyanate compound to introduce an isocyanate group into the polymer, and then the hydroxyl group and ( A (meth)acryloyl group can also be introduced by reacting a compound having a meth)acryloyl group.
  • the diisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like.
  • the compound having a hydroxyl group and a (meth)acryloyl group include, for example, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acryl acid esters, polypropylene glycol mono(meth)acrylic acid esters, and the like.
  • an acid anhydride is reacted with a polyoxyalkylene polymer having a hydroxyl group to introduce a carboxyl group into the polymer, followed by epoxy
  • a (meth)acryloyl group can also be introduced by reacting the group with a compound having a (meth)acryloyl group.
  • the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl anhydride.
  • Specific examples of the compound having an epoxy group and a (meth)acryloyl group include glycidyl (meth)acrylate.
  • Still another example of the method for synthesizing the polyfunctional macromonomer (b2′′) is a method of dehydration condensation of methacrylic acid and acrylic acid on a polyoxyalkylene polymer having a hydroxyl group.
  • methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, etc. are reacted with a polyoxyalkylene polymer having a hydroxyl group. There is a way.
  • the number average molecular weight of the polyfunctional macromonomer (b2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesiveness exhibited by the cured product and the ease of handling of (b2). ,000 or more is more preferable, and 2,000 or more is even more preferable. Also, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less.
  • the weight average molecular weight of the polyfunctional macromonomer (b2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesiveness exhibited by the cured product and the ease of handling of (b2). ,000 or more is preferable, and 2,500 or more is more preferable. Also, it is preferably 130,000 or less, more preferably 65,000 or less, even more preferably 60,000 or less, and even more preferably 30,000 or less.
  • the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polyfunctional macromonomer (b2) is not particularly limited, but is preferably narrow, specifically less than 2.0. 6 or less is more preferable, 1.5 or less is more preferable, 1.4 or less is even more preferable, 1.3 or less is particularly preferable, and 1.2 or less is most preferable.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyfunctional macromonomer (b2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.
  • the (meth)acrylic acid ester-based copolymer (B) is a molecular chain mainly composed of the (meth)acrylic acid ester (b1) and a molecule derived from the main chain skeleton of the polyfunctional macromonomer (b2). have chains. Since the polyfunctional macromonomer (b2) has more than one (meth)acryloyl group in one molecule, which is a polymerizable group, the (meth)acrylate copolymer (B) is a polyfunctional macro It may have a structure in which more than one molecular chain mainly composed of the (meth)acrylic acid ester (b1) is bonded to one molecular chain derived from the main chain skeleton of the monomer (b2).
  • the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (b2) is introduced into either the terminal or the side chain (non-terminal portion) of the molecular chain mainly composed of the (meth)acrylic acid ester (b1). However, from the viewpoint of adhesiveness, it is preferably introduced into the side chain.
  • an H-type structure can be formed in which molecular chains composed mainly of (meth)acrylic acid ester (b1) are bonded.
  • the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (b2) corresponds to the horizontal bar of H, and the molecular chain mainly composed of the (meth)acrylic acid ester (b1) Corresponds to the two vertical bars included.
  • the H-shaped structure will be described later.
  • the content of the polyfunctional macromonomer (b2) is preferably 1% by weight or more and 70% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (B). , 5 wt % or more and 60 wt % or less, more preferably 10 wt % or more and 50 wt % or less, and particularly preferably 15 wt % or more and 45 wt % or less.
  • the content of the polyfunctional macromonomer (b2) is preferably less than 35% by weight.
  • the content of the polyfunctional macromonomer (b2) is preferably 35% by weight or more.
  • the content of the polyfunctional macromonomer (b2) is 0.05 mol% or more and 6.0 mol% or less in the monomer components constituting the (meth)acrylate copolymer (B). It preferably accounts for 0.1 mol % or more and 2.3 mol % or less, and even more preferably 0.2 mol % or more and 1.5 mol % or less. Within the above range, the effects of using the polyfunctional macromonomer (b2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylate copolymer (B).
  • the average number of polyfunctional macromonomers (b2) per molecule of the (meth)acrylate copolymer (B) is 0.05 or more and 2.0 or less from the viewpoint of the strength of the resulting cured product. is preferred.
  • the lower limit is more preferably 0.07 or more, and even more preferably 0.08 or more.
  • the upper limit is more preferably 1.5 or less, even more preferably 1.0 or less.
  • the average number can be calculated by the following formula.
  • a polyfunctional macromonomer (b2) is used by including a chain transfer agent (b3) having a mercapto group in the monomer component constituting the (meth)acrylate copolymer (B). Nevertheless, the molecular weight distribution of the (meth)acrylic acid ester copolymer (B) is relatively narrowed, and gelation is suppressed when synthesizing the (meth)acrylic acid ester copolymer (B). can do. In addition, it becomes possible to preferentially synthesize a polymer molecule in which one molecule of the polyfunctional macromonomer (b2) is introduced into one molecule of the (meth)acrylate copolymer (B).
  • the chain transfer agent (b3) having a mercapto group may not have a reactive silicon group, but preferably has a reactive silicon group.
  • the reactive silicon group is a reactive silicon group represented by formula (1) described above.
  • a reactive silicon group can be introduced at the end of the molecular chain mainly composed of the (meth)acrylic acid ester (b1). .
  • chain transfer agent (b3) having a mercapto group is not particularly limited, examples thereof include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane. , n-dodecylmercaptan, tert-dodecylmercaptan, laurylmercaptan and the like.
  • the content of the chain transfer agent (b3) having a mercapto group is 1% by weight or more and 15% by weight or less with respect to the total amount of the monomer components constituting the (meth)acrylate copolymer (B). is preferred, more preferably 2 wt % or more and 10 wt % or less, and more preferably 3 wt % or more and 8 wt % or less.
  • the content of the chain transfer agent (b3) having a mercapto group accounts for 0.1 mol% or more and 20 mol% or less of the monomer components constituting the (meth)acrylate copolymer (B). preferably 0.4 mol% or more and 15 mol% or less, more preferably 0.5 mol% or more and 10 mol% or less, and 0.6 mol% or more and 8 mol% or less is particularly preferred. Within the above range, the effect of using the chain transfer agent (b3) having a mercapto group can be achieved.
  • the content of the polyfunctional macromonomer (b2) and the content of the chain transfer agent (b3) having a mercapto group improve the strength of the resulting cured product, so the polyfunctional macromonomer (b2)/mercapto group
  • the molar ratio of the chain transfer agent (b3) to have is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.09 or more, and particularly preferably 0.1 or more.
  • the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.
  • the (meth)acrylic ester-based copolymer (B) may have a substituent derived from the chain transfer agent (b3) having a mercapto group (structure represented by —S—R 8 described later). Therefore, it may contain sulfur atoms.
  • the sulfur atom concentration in the (meth)acrylate copolymer (B) is preferably 700 ppm or more and 20,000 ppm or less, more preferably 1,000 ppm or more and 15,000 ppm or less.
  • the method for measuring the sulfur atom concentration is not particularly limited. It can be measured by known elemental analysis methods such as organic elemental analysis and fluorescent X-ray analysis. Further, the sulfur atom concentration is calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (B) and the amount (b3) of the chain transfer agent having a mercapto group. It may be a theoretical value.
  • the monomer (b4) having a reactive silicon group and a polymerizable unsaturated group is an arbitrary monomer and may not be used, but is preferably used.
  • the reactive silicon group possessed by the monomer (b4) is the reactive silicon group represented by formula (1) described above.
  • Examples of the monomer (b4) having a reactive silicon group and a polymerizable unsaturated group include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-( Compounds having a (meth)acryloxy group and a reactive silicon group, such as meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples include compounds having a vinyl group and a reactive silicon group such as triethoxysilane. These compounds may use only 1 type and may use 2 or more types together.
  • the content of the monomer (b4) is 0.1 weight with respect to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (B). % or more and 50 wt % or less, more preferably 0.5 wt % or more and 30 wt % or less, even more preferably 1 wt % or more and 20 wt % or less, and particularly preferably 2 wt % or more and 15 wt % or less. Moreover, the content of the monomer (b4) is preferably 10% by weight or less from the viewpoint of improving the thixotropy of the curable composition and obtaining a cured product with high elongation.
  • the monomer component constituting the (meth)acrylic acid ester copolymer (B) contains another monomer (b5) that does not correspond to any of (b1) to (b4) described in detail above. It may contain, or may not contain.
  • Other monomers (b5) include (meth)acrylic esters (b1) and monomers (b4) having a reactive silicon group and a polymerizable unsaturated group (meth)acrylic monomers and monomers other than the (meth)acrylic monomer. Specifically, other monomers described above for multifunctional macromonomer (b2') can be used.
  • the number average molecular weight of the (meth)acrylic acid ester copolymer (B) is not particularly limited, but is preferably 500 or more and 50,000 or less, preferably 500 or more and 30,000 or less, in terms of polystyrene equivalent molecular weight by GPC measurement. More preferably, 1,000 or more and 10,000 or less are particularly preferable. Among them, the number average molecular weight is preferably 7,000 or less because a (meth)acrylic acid ester copolymer (B) having a low viscosity can be obtained. In addition, the number average molecular weight is preferably 3,500 or less because good adhesiveness can be exhibited with low viscosity.
  • the weight average molecular weight of the (meth)acrylic acid ester copolymer (B) is not particularly limited, but is preferably 500 or more and 80,000 or less, preferably 3,000 or more and 70,000, in terms of polystyrene equivalent molecular weight by GPC measurement. The following are more preferable, and 5,000 or more and 65,000 or less are particularly preferable. Among them, the weight-average molecular weight is preferably 20,000 or less because a cured product having a low viscosity and a high strength can be obtained.
  • the value calculated by the following formula is 1.1 or more. is preferred.
  • the fact that the value calculated by the above formula is 1.1 or more means that the average number of introduction of the polyfunctional macromonomer (b2) in one molecule of the (meth)acrylic acid ester copolymer (B) is large. It means that the strength of the resulting cured product can be further improved.
  • the value calculated by the above formula is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more.
  • the upper limit is not particularly limited, it is preferably 10 or less, more preferably 5 or less.
  • the molecular weight distribution of the (meth)acrylic acid ester copolymer (B) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (B) low in viscosity, it ranges from 3.0 to 11.0. The following is preferable, 3.2 to 10.0 is more preferable, and 3.4 to 8.0 is even more preferable.
  • the molecular weight distribution of the (meth)acrylate copolymer (B) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the (meth)acrylate copolymer (B) may contain a triblock copolymer.
  • the triblock copolymer comprises a structure in which two first molecular chains are linked via one second molecular chain.
  • the first molecular chain is mainly composed of a molecular chain obtained by polymerizing the (meth)acrylic acid ester (b1), and the second molecular chain is composed of the main chain skeleton of the polyfunctional macromonomer (b2). .
  • the first molecular chain is a molecular chain formed by copolymerization of (b1), (meth)acryloyl groups in (b2), (b3), optional (b4), and optional other monomers. .
  • a reactive silicon group is attached to this first molecular chain.
  • the chain transfer agent (b3) having a mercapto group has a reactive silicon group
  • a monomer (b4) is used, a reactive silicon group is attached to the non-terminal portion of the first molecular chain.
  • the second molecular chain corresponds to the main chain skeleton of the (meth)acrylate polymer or polyoxyalkylene polymer in the polyfunctional macromonomer (b2).
  • the bonding method of two first molecular chains and one second molecular chain is different from that of ordinary ABA-type triblock copolymers, and both ends of the second molecular chain are respectively non-terminal sites of the first molecular chain.
  • the triblock copolymer comprises an H-type structure, where two vertical bars in H correspond to two first molecular chains and one horizontal bar in H corresponds to one second molecular chain. It corresponds to a molecular chain.
  • the (meth)acrylic acid ester-based copolymer (B) is not limited to a triblock copolymer with an H-type structure, and in addition to a triblock copolymer with an H-type structure, It may contain a block copolymer having Block copolymers having such other structures include, for example, block copolymers having a structure in which three first molecular chains are bonded via two second molecular chains.
  • the first molecular chain and the second molecular chain have an ester bond derived from the (meth)acryloyl group in the polyfunctional macromonomer (b2) (that is, an ester bond corresponding to the ester bond in the formula (4)). are connected through
  • the first molecular chain is composed of a hard polymer and the second molecular chain is composed of a soft polymer, it is preferable because a cured product with high strength and high elongation can be obtained.
  • a hard polymer refers to a polymer with a high glass transition temperature.
  • a soft polymer refers to a polymer with a low glass transition temperature.
  • the monomer components constituting the first molecular chain are methacrylic acid esters, It preferably contains at least one monomer selected from the group consisting of isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate.
  • the ratio of the monomers to the total amount of monomer components constituting the first molecular chain is preferably 60% by weight or more, more preferably 70% by weight or more. The upper limit may be 100% by weight.
  • the second molecular chain when the second molecular chain is composed of a soft polymer, the second molecular chain may be the main chain skeleton of a polyoxyalkylene-based polymer, or a (meth)acrylic acid ester-based polymer.
  • the monomer component constituting the second molecular chain (the monomer component forming the main chain skeleton of (b2′)) is an acrylate ester (however, isobornyl acrylate, dicycloacrylate excluding pentenyl and dicyclopentanyl acrylate).
  • the acrylic acid ester accounts for preferably 60% by weight or more, more preferably 70% by weight or more, of the monomer components constituting the second molecular chain.
  • the upper limit may be 100% by weight.
  • the first molecular chain is a molecular chain formed by reacting a chain transfer agent (b3) having a mercapto group, at either end of the first molecular chain, as a substituent derived from (b3) , —SR 8 .
  • S represents a sulfur atom
  • R8 represents a hydrocarbon group which may have a reactive silicon group.
  • the hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and the like.
  • the said reactive silicon group is a reactive silicon group represented by Formula (1) mentioned above.
  • Specific examples of R 8 include reactive silicon group-containing methyl group, reactive silicon group-containing propyl group, n-dodecyl group, tert-dodecyl group, lauryl group and the like.
  • the molar ratio of the main chain skeleton of the polyfunctional macromonomer (b2) to the —SR 8 is preferably 0.03 or more, more preferably 0.05 or more, and 0.05 or more. 09 or more is more preferable, and 0.1 or more is particularly preferable.
  • the upper limit of the molar ratio is not particularly limited, it is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.
  • the (meth)acrylate copolymer (B) can be produced by polymerizing the above monomer components.
  • the polymerization method is not particularly limited, but may be general free radical polymerization. According to the present embodiment, although it is a free radical polymerization, it is possible to control the polymerization, and it is possible to produce a (meth)acrylic acid ester copolymer (B) that is a block copolymer. , its molecular weight distribution can be relatively narrow.
  • Polymerization initiators that can be used in the free radical polymerization include, for example, 2,2′-azobis(2-methylbutyronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2 '-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis [N- (2-propenyl) -2- methyl propionamide], 1,1'-azobis (cyclohexane-1-carbonitrile) and other azo compounds; benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, para diacyl peroxides such as chlorobenzoyl peroxide and di(3,5,5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2
  • solvents that can be used in the free radical polymerization include aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; hexane, Aliphatic hydrocarbon solvents such as heptane, octane, cyclohexane, and methylcyclohexane; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate, and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dimethyl carbonate, diethyl carbonate, etc.
  • aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-eth
  • alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol; Among them, alcohol compounds are preferable because they have a narrow molecular weight distribution.
  • Aromatic solvents are preferred because of their high dissolving power.
  • Aliphatic hydrocarbon solvents are preferred because of their low odor.
  • the molecular weight distribution of the (meth)acrylate copolymer (B) is affected by the amount of the chain transfer agent (b3) added and the solvent. When the amount of chain transfer agent (b3) added is 3% by weight or less, it is greatly affected by the type of solvent. When it is desired to obtain a (meth)acrylic acid ester copolymer (B) with a narrow molecular weight distribution, isobutanol is preferably used as the solvent.
  • the (meth)acrylic acid ester copolymer (B) uses a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, or reacts in addition to a mercapto group.
  • a chain transfer agent (b3) having a reactive silicon group it will have a reactive silicon group. Both methods may be used in combination.
  • a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group reactive silicon is randomly added to the side chains of the molecular chain mainly composed of (meth)acrylic acid ester (b1) groups can be introduced.
  • a chain transfer agent (b3) having a reactive silicon group in addition to a mercapto group a reactive silicon group is added to the end of the molecular chain mainly composed of the (meth)acrylic acid ester (b1). can be introduced.
  • a method of reacting an isocyanate silane compound having a reactive silicon group, or after copolymerizing glycidyl acrylate, an aminosilane compound having a reactive silicon group is used.
  • a method of reacting can be exemplified.
  • a (meth)acrylic ester copolymer obtained by a living radical polymerization method is easy to introduce a functional group into the terminal of the polymer, and by modifying this, a reactive silicon group can be introduced into the terminal of the polymer.
  • Examples of the compound having a reactive silicon group and a functional group that reacts with group V used in method (iii) include 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
  • any modification reaction can be used.
  • a method of blending a (meth)acrylic acid ester copolymer (B) and a polyoxyalkylene polymer (A) is disclosed in JP-A-59-122541, JP-A-63-112642, and JP-A-6. -172631, Japanese Patent Application Laid-Open No. 11-116763, and the like.
  • a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can be used.
  • the weight ratio (A):(B) of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B) is 95:5 to 10:90, that is, the weight ratio of (A)
  • the proportion is preferably 10% by weight or more and 95% by weight or less.
  • the ratio (A):(B) is preferably 80:20 to 20:80, more preferably 70:30 to 30:70.
  • the upper limit may be 50:50.
  • the ratio is preferably 50:50 to 20:80, more preferably 45:55 to 30:70.
  • the plasticizer (C) is an optional component, but is preferably blended with the B agent. It may be blended only in the B agent, or may be blended in each of the A agent and the B agent. Moreover, the plasticizer (C) may not be blended with the B agent and may be blended only with the A agent. Addition of the plasticizer (C) makes it possible to lower the viscosity of the curable composition and facilitate handling. In particular, by blending in the B agent, mixing of the A agent and the B agent can be easily realized.
  • the plasticizer (C) may not be blended with the B agent, and instead, the polyoxyalkylene polymer (A) and/or the epoxy resin (D) described above may be blended with the B agent. In addition, the plasticizer (C), the polyoxyalkylene polymer (A) and/or the epoxy resin (D) may be blended in the B agent. In addition, when the B agent contains the polyoxyalkylene polymer (A), the polyoxyalkylene polymer (A) contained in the A agent and the polyoxyalkylene polymer (A) contained in the B agent are the same. It may be one, or it may be different.
  • the plasticizer (C) is not particularly limited, and examples thereof include phthalates such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butylbenzyl phthalate.
  • phthalates such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butylbenzyl phthalate.
  • terephthalic acid ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, sebacin Aliphatic polyvalent carboxylic acid ester compounds such as dibutyl acid, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phosphoric acid ester compounds; trimellitic acid ester compounds chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oil; epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-ep
  • a polymeric plasticizer can also be used as the plasticizer (C).
  • polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyether plasticizers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
  • polymer plasticizers are preferred, polyether plasticizers are more preferred, and polypropylene glycol is particularly preferred.
  • the plasticizer (C) only one type may be used, or two or more types may be used in combination.
  • the total blending amount of the plasticizer (C) is 5 to 150 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). is preferred, 10 to 120 parts by weight is more preferred, and 20 to 100 parts by weight is particularly preferred.
  • the epoxy resin (D) is an optional component, but when blended, it is preferably blended with the B agent.
  • Commonly used epoxy resins can be used as the epoxy resin (D).
  • epichlorohydrin-bisphenol A type epoxy resin epichlorohydrin-bisphenol F type epoxy resin
  • flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin
  • hydrogenated bisphenol A type epoxy resin bisphenol A propylene oxide adduct glycidyl ether type epoxy resin
  • p-oxybenzoic acid glycidyl ether ester type epoxy resin m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxies Resin, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine,
  • an epoxy resin having at least two epoxy groups in one molecule is preferable because it has high reactivity during curing and the cured product can easily form a three-dimensional network. More preferred are bisphenol A type epoxy resins and novolac type epoxy resins.
  • the amount of the epoxy resin (D) used is the total of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B), and the weight ratio of the epoxy resin (D) [(A+B): (D)] is 90:10 to 50:50, that is, the ratio of (A+B) is preferably 50% by weight or more and 90% by weight or less. From the viewpoint of the flexibility of the cured product, it is preferably 50% by weight or more, and from the viewpoint of the strength of the cured product, it is preferably 90% by weight or less. Furthermore, 80:20 to 60:40 is more preferable in terms of balance between flexibility and strength.
  • epoxy resin curing agent (E) ⁇ epoxy resin curing agent (E)>>
  • the epoxy resin curing agent (E) is preferably blended in a different agent from the agent in which the epoxy resin (D) is blended, and more specifically, blended in the A agent.
  • epoxy resin curing agent (E) it is preferable to use an epoxy resin curing agent having a tertiary amine.
  • an epoxy resin curing agent having a tertiary amine By using an epoxy resin curing agent having a tertiary amine, a cured product with high rigidity, high strength and high elongation can be obtained.
  • any compound having a tertiary amine can be used.
  • the epoxy resin curing agent having a tertiary amine is preferably an aromatic amine, and more preferably has three or more amino groups.
  • 2,4,6-tris(dimethylaminomethyl)phenol can be exemplified.
  • the amount of the epoxy resin curing agent (E) used is preferably 0.1 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the epoxy resin (D). It is more preferably 0.5 parts by weight or more and 30 parts by weight or less.
  • Water (F) is an optional component, but is preferably blended.
  • water (F) when using the curable composition according to the present embodiment, the reactive silicon of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester copolymer (B) The hydrolysis reaction of the group is promoted, and the initial development of adhesive strength is improved.
  • Water (F) may be blended with either agent A or agent B, but is preferably blended with agent B. According to this aspect, it is possible to avoid deterioration of the storage stability of the agent A containing the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester copolymer (B).
  • the amount of water (F) added is, from the viewpoint of initial adhesive strength development, with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester copolymer (B). It is preferably from 0.1 to 10 parts by weight, more preferably from 0.3 to 5 parts by weight, and even more preferably from 0.5 to 3 parts by weight.
  • the ratio of water (F) to the total amount of agent B is preferably 0.5 to 30% by weight. Within this range, mixing of the A agent and the B agent can be easily achieved. It is more preferably 1 to 20% by weight, still more preferably 2 to 15% by weight.
  • silanol condensation catalyst (G) is an optional component, but it promotes the condensation reaction of the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). Since it is possible, it is preferable to be blended.
  • the silanol condensation catalyst (G) may be blended with either the A agent or the B agent, or may be blended with both.
  • silanol condensation catalyst (G) examples include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
  • organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds.
  • reaction product with dibutyltin oxide and phthalate ester dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), dioctyltin distearate, dioctyltin oxide, a reaction product of dioctyltin oxide and a silicate compound, and the like.
  • carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
  • carboxylic acid metal salt the following carboxylic acid and various metals can be combined.
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5 - nitrogen-containing heterocyclic compounds such as diazabicyclo[4,3,0]nonene-5(DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide biguanides such as; amino group-containing silane coupling agents; and ketimine compounds.
  • amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine
  • pyridine 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5 - nitrogen-containing heterocyclic compounds
  • carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetonate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetate.
  • titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetonate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetate.
  • Aluminum compounds such as acetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), and the like.
  • fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
  • the silanol condensation catalyst may be used in combination of two or more different catalysts.
  • the combined use of the amine compound and carboxylic acid, or the combined use of the amine compound and alkoxy metal has the effect of improving reactivity. may be obtained.
  • the amount of the silanol condensation catalyst (G) used is, from the viewpoint of promoting the condensation reaction of reactive silicon groups, the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester copolymer (B) of 100 weight. It is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and even more preferably 0.01 to 10 parts by weight.
  • the curable composition according to the present embodiment includes a polyoxyalkylene polymer (A), a (meth)acrylic acid ester copolymer (B), a plasticizer (C), an epoxy resin (D), an epoxy resin
  • a polyoxyalkylene polymer A
  • B a (meth)acrylic acid ester copolymer
  • C plasticizer
  • D an epoxy resin
  • E curing agent
  • F water
  • G silanol condensation catalyst
  • additives such as fillers, adhesion imparting agents, dehydrating agents, rheology control agents, antioxidants, light stabilizers, ultraviolet rays Absorbents, tackifying resins, and other resins may be added.
  • additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the curable composition or cured product.
  • additives include solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, ozone Degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents and the like.
  • a filler can be blended into the curable composition. It may be blended with the A agent or may be blended with the B agent. It may be blended in each of the A agent and the B agent. The strength of the cured product can be improved by adding a filler.
  • Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, Alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.
  • Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition. Only one type of filler may be used, or two or more types may be used in combination.
  • the amount of filler used is preferably 1 to 300 parts by weight, preferably 10 to 250 parts by weight, with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). Parts by weight are more preferred.
  • the curable composition may contain an adhesive agent. It may be blended in the A agent or the B agent, but is preferably blended in the A agent. A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
  • Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used.
  • the adhesion imparting agent may be used alone or in combination of two or more.
  • the amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). , more preferably 0.5 to 10 parts by weight.
  • a dehydrating agent can be added to the curable composition.
  • a dehydrating agent is preferably added to the A agent to improve the stability of the A agent.
  • the dehydrating agent is preferably a compound that can react with water, more preferably a silicon compound that can react with water (excluding compounds corresponding to adhesiveness-imparting agents), and particularly a trialkoxysilane compound. preferable.
  • dehydrating agent examples include vinyl group-containing silanes such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldimethoxysilane. and the like. Only one type of dehydrating agent may be used, or two or more types may be used.
  • the amount of dehydrating agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester copolymer (B). .5 to 10 parts by weight is more preferred, and 1 to 5 parts by weight is even more preferred.
  • a rheology control agent may be added to the curable composition to prevent sagging and improve workability. It may be blended in the A agent or the B agent, but is preferably blended in the A agent.
  • rheology control agent is not particularly limited, examples thereof include fatty acid amide waxes, hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; dry silica, wet silica, and the like. These rheology control agents may be used alone or in combination of two or more.
  • the amount of the rheology control agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B).
  • An antioxidant can be used in the curable composition.
  • the use of an antioxidant can enhance the weather resistance of the cured product.
  • antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of antioxidant used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). 0.2 to 5 parts by weight is more preferred.
  • a light stabilizer can be used in the curable composition.
  • the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
  • Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
  • the amount of light stabilizer used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). 0.2 to 5 parts by weight is more preferred.
  • a UV absorber can be used in the curable composition.
  • the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
  • UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds.
  • Benzotriazole-based compounds are particularly preferred, and are commercially available as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B). 0.2 to 5 parts by weight is more preferred.
  • a physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition, if necessary.
  • the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
  • arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; silyl)borates; silicone varnishes; and polysiloxanes.
  • the physical property modifier By using the physical property modifier, the hardness of the cured curable composition according to the present embodiment can be increased, or conversely, the hardness can be decreased and elongation at break can be increased.
  • the physical property modifiers may be used alone or in combination of two or more.
  • a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without exacerbating the stickiness of the surface of the cured product.
  • Compounds that generate trimethylsilanol are particularly preferred.
  • examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups.
  • Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
  • the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester copolymer (B). 0.5 to 5 parts by weight is more preferred.
  • a tackifier resin can be added to the curable composition for the purpose of enhancing the adhesiveness or adhesion to the substrate, or for other purposes.
  • Specific examples of tackifying resins include terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, and coumarone-indene.
  • the amount of the tackifying resin used is preferably 2 to 100 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B), and 5 to 100 parts by weight. 50 parts by weight is more preferred, and 5 to 30 parts by weight is even more preferred.
  • the curable composition according to the present embodiment comprises an A agent containing at least a polyoxyalkylene polymer (A) and an acrylic acid ester copolymer (B), a polyoxyalkylene polymer (A) and a plasticizer It is composed of (C) and a B agent containing at least one of the epoxy resins (D), and is preferably prepared as a multi-liquid type in which the A agent and the B agent are mixed before use.
  • the curable composition according to this embodiment may be cured at room temperature or may be cured by heating.
  • the heating temperature is not particularly limited, but is preferably 40° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher. However, if the temperature rises to 100°C or higher, the water in agent B evaporates and may cause voids, so the heating temperature is preferably lower than 100°C.
  • the curable composition according to this embodiment can exhibit good adhesion to various adherends such as plastics, metals and composite materials.
  • adherends such as plastics, metals and composite materials.
  • non-polar materials such as polypropylene and engineering plastics having rigid molecular chains such as polyphenylene sulfide
  • the adherend can be previously surface-treated by known methods. For example, surface treatment techniques such as sanding, flame treatment, corona discharge, arc discharge, plasma treatment, etc. can be used. Plasma treatment is preferred because it causes little damage to the adherend and provides stable adhesion. These surface treatments are also effective for removing release agents used during molding and remaining on the adherend surface.
  • the curable composition according to a preferred embodiment exhibits the desired physical properties by performing a long-term curing (curing) step after bonding the adherend, while the long-term curing step is performed before It may have the property that the initial adhesive strength is relatively high. Therefore, the curable composition can be suitably used for bonding adherends in a continuous line production system.
  • the conditions of the final curing (curing) step for the curable composition to express the final desired physical properties are not particularly limited, but for example, the temperature is 5 to 90 ° C. and the time is 24 hours to 1 week. be done.
  • the curable composition is suitable for use as an adhesive composition, sealing materials for buildings, ships, automobiles, roads, etc., adhesives for joining panels of buses, trailers, trains, etc., adhesives, waterproofing. It can be used for materials.
  • the curable compositions are also suitable for joining dissimilar materials such as aluminum-steel, steel-composites, and aluminum-composites. When dissimilar materials are joined, it is preferable to cover the joint with a sealer to prevent corrosion.
  • a sealer it is possible to use a polymer having reactive silicon groups as shown in this application.
  • Applications in which the curable composition is used include automotive parts such as vehicle panels, large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, ship parts, electrical parts, and various machine parts. It is preferably used as an adhesive.
  • a multi-component curable composition comprising agent A and agent B, Agent A contains a polyoxyalkylene polymer (A) having a reactive silicon group, and a (meth)acrylic acid ester copolymer (B) having a reactive silicon group, Agent B contains at least one compound selected from the group consisting of a polyoxyalkylene polymer (A) having a reactive silicon group, a plasticizer (C), and an epoxy resin (D),
  • the monomer component constituting the (meth)acrylic acid ester copolymer (B) is (meth) acrylic acid ester (b1), A polymer (b2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (b3) having a mercapto group,
  • the monomer component further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, and/or the
  • [Item 5] 5 The multi-component curable composition according to any one of items 1 to 4, wherein the polyoxyalkylene polymer (A) has a terminal structure represented by the general formula (2).
  • [Item 6] 6 The multicomponent curable composition according to any one of items 1 to 5, wherein the main chain structure of the polyoxyalkylene polymer (A) is branched.
  • the B agent further contains water (F).
  • agent B contains, as the compound, a polyoxyalkylene polymer (A) having a reactive silicon group.
  • agent B contains, as the compound, a polyoxyalkylene polymer (A) having a reactive silicon group.
  • B agent contains a plasticizer (C) as the compound.
  • C plasticizer
  • B agent contains an epoxy resin (D) as the compound.
  • D epoxy resin
  • the number average molecular weight and weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.
  • Liquid delivery system Tosoh HLC-8120GPC
  • Column TSK-GEL H type manufactured by Tosoh Solvent: THF
  • Molecular weight Polystyrene equivalent Measurement temperature: 40°C
  • the terminal group equivalent molecular weights in the examples were obtained by determining the hydroxyl value by the measurement method of JIS K 1557, the iodine value by the measurement method of JIS K 0070, and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). It is the molecular weight obtained by taking into consideration.
  • the average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer shown in the examples was calculated by the following formula.
  • (Average introduction number) [Unsaturated group concentration of polymer determined from iodine value (mol/g) - Unsaturated group concentration of precursor polymer determined from iodine value (mol/g)]/[Determined from hydroxyl value Hydroxyl group concentration of precursor polymer (mol/g)]
  • the average number of reactive silicon groups introduced per terminal of the polymer (A) shown in Examples was calculated by NMR measurement.
  • the sulfur atom concentration is a theoretical value calculated from the total amount of the monomer components used in the production of the (meth)acrylate copolymer (B) and the amount of the chain transfer agent (b3) having a mercapto group. be.
  • Synthesis example 1 Polyoxypropylene triol having a number average molecular weight of about 4,020 (molecular weight as converted to terminal group: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 26,200 ( A polyoxypropylene triol having a terminal group-equivalent molecular weight of 17,440 was obtained. Sodium methoxide was added as a 28% methanol solution in an amount of 1.0 molar equivalent to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene.
  • Synthesis example 2 Polyoxypropylene triol having a number average molecular weight of about 4,020 (molecular weight as converted to terminal group: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 26,200 ( A polyoxypropylene triol having a terminal group-equivalent molecular weight of 17,440 was obtained. Subsequently, a methanol solution of 1.2 equivalents of NaOMe is added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene triol to distill off the methanol, and 1.5 equivalents of 3-chloro-1-propene is added.
  • a linear reactive silicon group-containing polyoxypropylene polymer (A-3) having an average number of silicon groups of 3.2 and a number average molecular weight of 14,600 was thus obtained.
  • the filtrate was concentrated under reduced pressure, and the polymer having an acryloyl group at one end (that is, having one acryloyl group in one polymer molecule) had a number average molecular weight of 10,700 (GPC molecular weight) and a molecular weight distribution (Mw/Mn) of A macromonomer (p-1), which is a (meth)acrylic acid ester-based polymer with a polymer of 1.18, was obtained.
  • the macromonomer (p-1) does not correspond to the polyfunctional macromonomer (b2).
  • the solution was added dropwise over 5 hours. Further, a mixed solution of 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 7.8 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-1) having a molecular weight of 290 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.069 mmol/g, a reactive silicon group equivalent weight of 0.72 mmol/g, and a sulfur atom concentration of 10,920 ppm.
  • An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-2) having a molecular weight of 750 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.031 mmol/g, a reactive silicon group equivalent weight of 0.56 mmol/g, and a sulfur atom concentration of 9,453 ppm.
  • a mixed solution dissolved in .3 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 5.5 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-3) having a molecular weight of 600 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.032 mmol/g, a reactive silicon group equivalent weight of 0.56 mmol/g, and a sulfur atom concentration of 9,584 ppm.
  • a mixed solution dissolved in .3 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 5.5 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-4) having a molecular weight of 360 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.015 mmol/g, a reactive silicon group equivalent weight of 0.56 mmol/g, and a sulfur atom concentration of 9,584 ppm.
  • a mixed solution dissolved in .4 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 4.7 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-5) having a molecular weight of 480 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.017 mmol/g, a reactive silicon group equivalent weight of 0.67 mmol/g, and a sulfur atom concentration of 9,584 ppm.
  • a mixed solution dissolved in .4 parts by weight was added dropwise over 5 hours. Further, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 5.2 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • An isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (B-6) having a molecular weight of 270 (GPC) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.018 mmol/g, a reactive silicon group equivalent weight of 0.65 mmol/g, and a sulfur atom concentration of 9,584 ppm.
  • An isobutanol solution (solid content: 60%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-1) having a molecular weight of 630 (GPC) was obtained.
  • the solid content of the solution has a macromonomer equivalent weight of 0.033 mmol/g, a reactive silicon group equivalent weight of 0.56 mmol/g, and a sulfur atom concentration of 9,453 ppm.
  • a mixed solution of 3 parts by weight and 1.6 parts by weight of 2,2′-azobis(2-methylbutyronitrile) dissolved in 14.3 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 11.6 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours.
  • 000 (GPC molecular weight)
  • an isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) was obtained.
  • the solid content of the solution has a reactive silicon group equivalent of 0.64 mmol/g and a sulfur atom concentration of 12,956 ppm.
  • Example 1 42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1, and the reactive silicon group-containing (meth) acrylic acid ester copolymer obtained in Synthesis Example 10 ( After mixing the isobutanol solution of B-1) so that the solid content was 28 parts by weight, the isobutanol was devolatilized by heating.
  • Nocrac CD antioxidant, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • ADEKA STAB AO-60 antioxidant, manufactured by ADEKA Co., Ltd.
  • DINP as a plasticizer (C) (Diisononyl phthalate, manufactured by Jplus Co., Ltd.) 4 parts by weight
  • CCR-S10 as a filler (colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.) 12.5 parts by weight, Asahi Thermal (carbon black, Asahi Carbon Co., Ltd.) )) 0.05 parts by weight
  • AEROSIL 300 hydroophilic fumed silica, manufactured by Nippon Aerosil Co., Ltd.
  • AEROSIL R202 hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.
  • jER828 bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • Nanox #30 heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.
  • NIPGEL CX-200 wet silica, manufactured by Tosoh Silica Co., Ltd.
  • R-820 titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.
  • Neostan U-810 as a silanol condensation catalyst (G) (Dioctyl tin dilaurate, manufactured by Nitto Kasei Co., Ltd.) 1 part by weight and 1.5 parts by weight of water (F) were mixed using a planetary mixer to obtain a B agent.
  • a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture.
  • Shear test A steel plate (SS400) used as an adherend was polished with sandpaper #400 and degreased with heptane. After applying a mixture of the A and B agents to one adherend, the other adherend was adhered so as to have a bonding area of 25 mm ⁇ 12.5 mm and a thickness of 0.5 mm. Using this lamination time as the starting time, after 1 hour under 23°C 50% RH conditions and after 7 days curing under 23°C 50% RH conditions, the shear bond strength is measured at a test speed of 10 mm / min. Together, the state of destruction was observed.
  • the state of failure was visually confirmed using CF as cohesive failure (destruction at the adhesive portion) and AF as interfacial failure (peeling at the interface between the adhesive and the adherend). When both are mixed, the ratio of each is shown. For example, when the cohesive failure rate is 50% and the interfacial failure rate is 50%, it is described as C50A50. Table 2 shows the results.
  • Example 2-3 Comparative Example 1-2
  • a mixture of agents A and B was obtained in the same manner as in Example 1, except that each formulation was mixed at the ratio shown in Table 2, and a shear test was performed in the same manner as in Example 1.
  • Table 2 shows the results.
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (B-1) or (B-2) used in Examples 1 to 3 was produced using a polyfunctional macromonomer (b2'). It is a thing.
  • the reactive silicon group-containing (meth) acrylic acid ester copolymer (P-1) used in Comparative Example 1 does not use the polyfunctional macromonomer (b2), instead (meth) It is manufactured using a macromonomer having one acryloyl group.
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (P-2) used in Comparative Example 2 uses both a polyfunctional macromonomer and a macromonomer having one (meth)acryloyl group. It was manufactured without
  • agent A contains a reactive silicon group-containing polyoxyalkylene polymer (A) and a reactive silicon group-containing (meth)acrylic acid ester copolymer (B), and agent B contains
  • the multicomponent curable compositions of Examples 1 to 3 containing the epoxy resin (D) were reactive silicon group-containing (meth)acrylic acid ester copolymers (P- Compared to the multi-component curable compositions of Comparative Examples 1 and 2 in which 1) or (P-2) was used in place of component (B), the initial (after 1 hour) adhesive strength was higher.
  • the adhesion strength after curing for 7 days at 23° C. and 50% RH is high, and the final adhesion is also good.
  • Example 4-5 Comparative Example 3
  • a mixture of agents A and B was obtained in the same manner as in Example 1, except that the silanol condensation catalyst (G) was added to agent A instead of agent B, and the respective ingredients were mixed in the proportions shown in Table 3.
  • a shear test was conducted in the same manner as in Example 1, except that the shear strength after 2 hours was measured. Table 3 shows the results.
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (B-3) or (B-4) used in Examples 4 and 5 is a polyfunctional macromonomer (b2') or (b2'')
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) used in Comparative Example 3 does not use the polyfunctional macromonomer (b2) It was manufactured in
  • agent A contains a reactive silicon group-containing polyoxyalkylene polymer (A) and a reactive silicon group-containing (meth)acrylic acid ester copolymer (B), and agent B contains The multicomponent curable compositions of Examples 4 and 5 containing the epoxy resin (D) were reactive silicon group-containing (meth)acrylic acid ester copolymers (P- It can be seen that the initial adhesive strength is higher than that of the multicomponent curable composition of Comparative Example 3 in which component 3) was used instead of component (B).
  • Example 6 60 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-3) obtained in Synthesis Example 3, and the reactive silicon group-containing (meth) acrylic acid ester copolymer obtained in Synthesis Example 12 ( After mixing the isobutanol solution of B-3) so that the solid content was 40 parts by weight, the isobutanol was devolatilized by heating.
  • Nocrac CD antioxidant, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • ADEKA STAB AO-60 antioxidant, manufactured by ADEKA Co., Ltd.
  • C plasticizer
  • Coal P-23 polypropylene glycol, manufactured by Mitsui Chemicals Co., Ltd.
  • CCR-S10 colloidal calcium carbonate, manufactured by Shiraishi
  • a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture.
  • Shear test A shear test was performed in the same manner as in Example 1, except that the shear strength after 2 hours was measured. Table 4 shows the results.
  • Example 7-9 Comparative Example 4
  • Example 7-9 A mixture of agents A and B was obtained in the same manner as in Example 6, except that each formulation was mixed at the ratio shown in Table 4, and a shear test was performed in the same manner as in Example 6. Table 4 shows the results.
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (B-3) or (B-4) used in Examples 6 to 9 is a polyfunctional macromonomer (b2′) or (b2′′)
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) used in Comparative Example 4 does not use the polyfunctional macromonomer (b2) It was manufactured in
  • agent A contains a reactive silicon group-containing polyoxyalkylene polymer (A) and a reactive silicon group-containing (meth)acrylic acid ester copolymer (B), and agent B contains
  • the multicomponent curable compositions of Examples 6 to 9 containing the plasticizer (C) are reactive silicon group-containing (meth) acrylic acid ester copolymers (P- It can be seen that the initial adhesive strength is higher than that of the multicomponent curable composition of Comparative Example 4 in which 3) was used instead of component (B).
  • Examples 10 to 12, Comparative Example 5 A mixture of agents A and B was obtained in the same manner as in Example 6, except that each formulation was mixed at the ratio shown in Table 5. Further, a shear test was conducted in the same manner as in Example 1, except that the shear strength was measured after curing for 2 hours at 23°C and 50% RH and after curing for 7 days at 23°C and 50% RH.
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (B-2) or (B-5) used in Examples 10 to 12 is a polyfunctional macromonomer (b2′) or (b2′′)
  • the reactive silicon group-containing (meth)acrylic acid ester copolymer (P-1) used in Comparative Example 5 does not use the polyfunctional macromonomer (b2) , was produced using a macromonomer having one (meth)acryloyl group instead.
  • agent A contains a reactive silicon group-containing polyoxyalkylene polymer (A) and a reactive silicon group-containing (meth)acrylic acid ester copolymer (B), and agent B contains
  • the multicomponent curable compositions of Examples 10 to 12 containing the plasticizer (C) are reactive silicon group-containing (meth) acrylic acid ester copolymers (P- Compared to the multicomponent curable composition of Comparative Example 5 in which 1) was used instead of the component (B), it was found that the adhesive strength was higher in the initial stage (after 2 hours). In addition, it can be seen that the adhesive strength after curing for 7 days at 23° C. and 50% RH is high, and the final adhesiveness is also good.
  • Example 13 60 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-3) obtained in Synthesis Example 3, and the reactive silicon group-containing (meth) acrylic acid ester copolymer obtained in Synthesis Example 15 ( After mixing the isobutanol solution of B-6) so that the solid content was 40 parts by weight, the isobutanol was devolatilized by heating.
  • Nocrac CD antioxidant, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • ADEKA STAB AO-60 antioxidant, manufactured by ADEKA Co., Ltd.
  • DINP as a plasticizer (C) (Diisononyl phthalate, manufactured by J-Plus Co., Ltd.) 19 parts by weight
  • DAW-45 alumina, average particle size 45 ⁇ m, manufactured by DENKA Co., Ltd.
  • DAW-05 alumina, average particle Diameter 5 ⁇ m, manufactured by DENKA Co., Ltd.
  • Asahi Thermal carbon black, manufactured by Asahi Carbon Co., Ltd.
  • TS740 hydrophobic fumed silica, (manufactured by CABOT) were mixed using a planetary mixer and
  • Methoxysilane, manufactured by Momentive 3 parts by weight, KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight as an adhesion imparting agent, silanol condensation As a catalyst (G), 2 parts by weight of Neostan S-1 (dioctyltin bistriethoxysilicate, manufactured by Nitto Kasei Co., Ltd.) was mixed to obtain agent A.
  • KBM-603 N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Neostan S-1 dioctyltin bistriethoxysilicate, manufactured by Nitto Kasei Co., Ltd.
  • jER828 bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • D epoxy resin
  • DAW-45 alumina, average particle size 45 ⁇ m, manufactured by DENKA Corporation
  • NIPGEL CX-200 wet silica, Tosoh Silica Co., Ltd.
  • R-820 titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.
  • water (F ) were mixed using a planetary mixer to obtain a B agent.
  • Agent A and agent B were filled in a two-liquid mixing cartridge (manufactured by NORDSON Co., Ltd.) so that the ratio of agent A to agent B was 10:1 (volume ratio). Using a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture. A shear test was conducted in the same manner as in Example 1, except that the shear strength was measured after 2 hours at 23°C and 50% RH. Table 6 shows the results.
  • Example 14 The amount of plasticizer (C) DINP (diisononyl phthalate, manufactured by J-Plus Co., Ltd.) was changed to 25 parts by weight, and the heat-dissipating filler was replaced with DAW-45 (alumina, average particle size 45 ⁇ m, DENKA ( Co., Ltd.) 270 parts by weight, DAW-05 (alumina, average particle size 5 ⁇ m, DENKA Co., Ltd.) 178 parts by weight, ASFP-20 (alumina, average particle size 0.2 ⁇ m, DENKA Co., Ltd.) 40 Parts by weight, changed to 40 parts by weight of BE033 (aluminum hydroxide, average particle size 3 ⁇ m, manufactured by Nippon Light Metal Co., Ltd.), and the amount of other filler Asahi Thermal (carbon black, manufactured by Asahi Carbon Co., Ltd.) was changed to 0.2 parts by weight, and the rheology control agent TS740 (hydrophobic fumed silic
  • jER828 bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • D epoxy resin
  • DAW-45 alumina, average particle size 45 ⁇ m, manufactured by DENKA Corporation
  • DAW-05 alumina, average particle size 5 ⁇ m, manufactured by DENKA Corporation
  • ASFP-20 alumina, average particle size 0.2 ⁇ m, manufactured by DENKA Corporation
  • A-187 (3-glycidoxypropyltrimethoxysilane, manufactured by Momentive) as a silane coupling agent 8 parts by weight
  • water 2 Parts by weight were mixed using a planetary mixer to obtain a B agent.
  • Agent A and agent B were filled in a two-liquid mixing cartridge (manufactured by NORDSON Co., Ltd.) so that the ratio of agent A to agent B was 4:1 (volume ratio). Using a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture. A shear test was conducted in the same manner as in Example 1, except that the shear strength was measured after 2 hours at 23°C and 50% RH. Table 6 shows the results.
  • thermocouple (HIOKI LR5021). The thermocouple was fixed on the surface of the center of the heat dissipating material with aluminum tape.
  • the surface temperature of the hot plate set at 80°C was 80.8°C as measured by this thermocouple.
  • the surface temperature of the heat dissipating material was determined 1 minute and 3 minutes after the start of the measurement, and the surface temperature of the heat dissipating material was measured after 1 minute and 3 minutes from the start of the measurement. Table 6 shows the results.
  • a sheet having a thickness of about 2 mm was prepared from a mixture of agents A and B, and cured at 23° C. and 50% RH for 7 days and then at 50° C. for 4 days.
  • the resulting sheet was punched into a No. 3 dumbbell type (JIS K 6251) and subjected to a tensile strength test at 23° C. and 50% RH to measure the strength at break (TB) and elongation at break (EB).
  • Tensile physical properties were measured using an Autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 50 mm/min. Table 6 shows the results.
  • the reactive silicon group-containing (meth)acrylate copolymer (B-6) used in Examples 13 and 14 was produced using a polyfunctional macromonomer (b2′′).
  • agent A contains a reactive silicon group-containing polyoxyalkylene polymer (A) and a reactive silicon group-containing (meth) acrylic acid ester copolymer (B), and agent B contains It can be seen that the multicomponent curable compositions of Examples 13 and 14 containing the epoxy resin (D) have high initial adhesive strength (after 2 hours). Moreover, it can be seen that the multi-component curable compositions of Examples 13 and 14 have good thermal conductivity and tensile physical properties after curing.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016216633A (ja) * 2015-05-21 2016-12-22 株式会社カネカ 硬化性組成物及びその硬化物
JP2017066349A (ja) * 2015-10-02 2017-04-06 株式会社カネカ 硬化性組成物
JP2021024958A (ja) * 2019-08-06 2021-02-22 株式会社カネカ 硬化性組成物
JP2021134276A (ja) * 2020-02-27 2021-09-13 株式会社カネカ 硬化性組成物
WO2022203065A1 (ja) * 2021-03-26 2022-09-29 株式会社カネカ 硬化性組成物及びその硬化物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016216633A (ja) * 2015-05-21 2016-12-22 株式会社カネカ 硬化性組成物及びその硬化物
JP2017066349A (ja) * 2015-10-02 2017-04-06 株式会社カネカ 硬化性組成物
JP2021024958A (ja) * 2019-08-06 2021-02-22 株式会社カネカ 硬化性組成物
JP2021134276A (ja) * 2020-02-27 2021-09-13 株式会社カネカ 硬化性組成物
WO2022203065A1 (ja) * 2021-03-26 2022-09-29 株式会社カネカ 硬化性組成物及びその硬化物

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