WO2023132324A1 - Curable composition and cured product thereof - Google Patents

Curable composition and cured product thereof Download PDF

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WO2023132324A1
WO2023132324A1 PCT/JP2022/048597 JP2022048597W WO2023132324A1 WO 2023132324 A1 WO2023132324 A1 WO 2023132324A1 JP 2022048597 W JP2022048597 W JP 2022048597W WO 2023132324 A1 WO2023132324 A1 WO 2023132324A1
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meth
group
weight
acrylate
curable composition
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French (fr)
Japanese (ja)
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters

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.
  • Curable compositions such as adhesives or pressure-sensitive adhesives containing an organic polymer having a reactive silicon group have a high viscosity in a relatively low temperature range and good fixability to the adherend, while being heated to a high temperature.
  • curable compositions such as adhesives or pressure-sensitive adhesives containing an organic polymer having a reactive silicon group have a high viscosity in a relatively low temperature range and good fixability to the adherend, while being heated to a high temperature.
  • there is a demand for physical properties such that the viscosity decreases and workability such as application to a base material is improved.
  • the present invention provides a curable composition containing an organic polymer having a reactive silicon group, which has a high viscosity at a relatively low temperature, but the viscosity is significantly reduced at a relatively high temperature.
  • An object of the present invention is to provide a curable composition capable of
  • a reactive silicon group-containing (meth)acrylic acid ester polymer is composed of a specific monomer and a chain transfer agent, and a tackifier
  • the inventors have found that the above problems can be solved by using a resin together, and have completed the present invention.
  • the present invention contains a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and a tackifying resin (B),
  • the monomer component constituting the (meth)acrylic acid ester copolymer (A) is (meth) acrylic acid ester (a1), A polymer (a2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (a3) having a mercapto group
  • the monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon It relates to a curable composition further comprising groups.
  • 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 curable composition.
  • a curable composition containing an organic polymer having a reactive silicon group which has a high viscosity at a relatively low temperature, can be cured so that the viscosity can be remarkably reduced at a relatively high temperature.
  • a sexual composition can be provided.
  • the curable composition according to the present invention can be suitably used as a hot-melt curable composition or an adhesive composition.
  • the curable composition according to this embodiment contains at least a (meth)acrylic acid ester copolymer (A) having a reactive silicon group and a tackifying resin (B).
  • the (meth)acrylic ester-based copolymer (A) has a reactive silicon group represented by the following general formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
  • —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 (meth)acrylate copolymer (A) 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 (A) 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 (A) includes at least a (meth)acrylic acid ester (a1), a polymer (a2) 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 (a3) having a group.
  • “(meth)acryl” means "acryl and/or methacryl”.
  • the (meth)acrylic ester-based copolymer (A) has reactive silicon groups by satisfying either one or both of the following two conditions.
  • Condition 1 The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group.
  • Condition 2 The chain transfer agent (a3) having a mercapto group further has a reactive silicon group.
  • a curable composition containing a reactive silicon group-containing (meth)acrylic acid ester copolymer (A) that satisfies the above requirements has a high viscosity at a relatively low temperature, but can be cured at a relatively high temperature. Then the viscosity can be significantly reduced.
  • 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 (a1) 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)
  • the content of the (meth)acrylic acid ester (a1) is 30% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). 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 (a1) 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 (A). 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 (a1) 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 (a2), 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 (a2) 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 (A). Since the polymer (a2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (a1). Moreover, since the polymer (a2) 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 (a2) is mainly composed of the (meth)acrylic acid ester (a1) in the (meth)acrylic acid ester-based copolymer (A) 2 It can form a structure that crosslinks the molecular chains (the first molecular chain described later).
  • the polymer (a2) is also referred to as polyfunctional macromonomer (a2).
  • the (meth)acryloyl group possessed by the polyfunctional macromonomer (a2) 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 (a2).
  • the polyfunctional macromonomer (a2) 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 (a2) 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 (a2) 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 (a2) 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 (a2) 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 (a2) is preferably a (meth)acrylate polymer or a polyoxyalkylene polymer.
  • the polyfunctional macromonomer (a2) whose main chain skeleton is a (meth)acrylic acid ester polymer is denoted as (a2′), and the main chain skeleton is a polyoxyalkylene polymer.
  • Macromonomer (a2) is denoted as (a2′′).
  • the monomer constituting the main chain skeleton of the polyfunctional macromonomer (a2') 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 (a2') is preferably composed of a soft polymer.
  • the monomer component forming the main chain skeleton of the polyfunctional macromonomer (a2′) is an acrylate ester (however, 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 (a2') 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 (a2′′) 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 (a2′′) 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.
  • a polyoxyalkylene polymer having a hydroxyl group is reacted with an acid anhydride 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 (a2′′) 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 (a2) 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 (a2). ,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 (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesive properties exhibited by the cured product and the ease of handling of (a2). ,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 (a2) 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 (a2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.
  • the (meth)acrylic acid ester-based copolymer (A) has a molecular chain mainly composed of the (meth)acrylic acid ester (a1) and a molecule derived from the main chain skeleton of the polyfunctional macromonomer (a2). have chains. Since the polyfunctional macromonomer (a2) has more than one (meth)acryloyl group in one molecule, which is a polymerizable group, the (meth)acrylic acid ester copolymer (A) is a polyfunctional macro It may have a structure in which more than one molecular chain mainly composed of the (meth)acrylic acid ester (a1) is bonded to one molecular chain derived from the main chain skeleton of the monomer (a2).
  • the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) 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 (a1). 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 (a1) are bonded.
  • the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) corresponds to the horizontal bar of H, and the molecular chain mainly composed of the (meth)acrylic acid ester (a1) Corresponds to the two vertical bars included.
  • the H-shaped structure will be described later.
  • the content of the polyfunctional macromonomer (a2) 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 (A). , 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 (a2) is preferably less than 35% by weight.
  • the content of the polyfunctional macromonomer (a2) is preferably 35% by weight or more.
  • the content of the polyfunctional macromonomer (a2) is 0.05 mol% or more and 6.0 mol% or less in the monomer components constituting the (meth)acrylate copolymer (A). 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 effect of using the polyfunctional macromonomer (a2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylate copolymer (A).
  • the average number of polyfunctional macromonomers (a2) per molecule of (meth)acrylic acid ester copolymer (A) 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 (a2) is used by including a chain transfer agent (a3) having a mercapto group in the monomer component constituting the (meth)acrylate copolymer (A). Nevertheless, the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is relatively narrowed, and gelation is suppressed when synthesizing the (meth)acrylic acid ester copolymer (A). can do. In addition, it becomes possible to preferentially synthesize a polymer molecule in which one molecule of the polyfunctional macromonomer (a2) is introduced into one molecule of the (meth)acrylate copolymer (A).
  • the chain transfer agent (a3) 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 (a1). .
  • chain transfer agent (a3) 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 (a3) 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 (A). 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 (a3) 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 (A). 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 (a3) having a mercapto group can be achieved.
  • the content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent (a3) having a mercapto group improve the strength of the resulting cured product, so that the polyfunctional macromonomer (a2)/mercapto group
  • the molar ratio of the chain transfer agent (a3) 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 acid ester copolymer (A) may have a substituent derived from the chain transfer agent (a3) having a mercapto group (structure represented by -SR 8 described later). Therefore, it may contain sulfur atoms.
  • the sulfur atom concentration in the (meth)acrylate copolymer (A) 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 (A) and the amount (a3) of the chain transfer agent having a mercapto group. It may be a theoretical value.
  • the monomer (a4) 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 (a4) is the reactive silicon group represented by formula (1) described above.
  • Examples of the monomer (a4) 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 (a4) is 0.1 weight with respect to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A) % 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.
  • the content of the monomer (a4) 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-based copolymer (A) contains another monomer (b5) that does not correspond to any of (a1) to (a4) detailed above. It may contain, or may not contain.
  • Other monomers (b5) include (meth)acrylic esters (a1) and monomers (a4) 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 (a2') can be used.
  • the number average molecular weight of the (meth)acrylic acid ester copolymer (A) 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)acrylate copolymer (A) 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 (A) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 or more and 80,000 or less, and 3,000 or more and 70,000. 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 (a2) in one molecule of the (meth)acrylic acid ester copolymer (A) 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 (A) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (A) low in viscosity, it is 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 (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the (meth)acrylate copolymer (A) 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 (a1), and the second molecular chain is composed of the main chain skeleton of the polyfunctional macromonomer (a2). .
  • the first molecular chain is a molecular chain formed by copolymerization of (a1), (meth)acryloyl groups in (a2), (a3), optional (a4), and optional other monomers. .
  • a reactive silicon group is attached to this first molecular chain.
  • the chain transfer agent (a3) having a mercapto group has a reactive silicon group
  • a reactive silicon group is bonded to the end of the first molecular chain, and a monomer having a reactive silicon group and a polymerizable unsaturated group
  • a4 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 (a2).
  • 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 (A) 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 (a2) (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 (a2′)) 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 the chain transfer agent (a3) having a mercapto group, at either end of the first molecular chain, as a substituent derived from (a3) , —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 (a2) 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 (A) 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, the polymerization can be controlled, and the (meth)acrylic acid ester copolymer (A), which is a block copolymer, can be produced. , 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 (A) is affected by the amount of the chain transfer agent (a3) added and the solvent. When the amount of chain transfer agent (a3) added is 3% by weight or less, it is greatly affected by the type of solvent. When it is desired to obtain a (meth)acrylate copolymer (A) with a narrow molecular weight distribution, isobutanol is preferably used as the solvent.
  • the (meth)acrylic acid ester copolymer (A) uses a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, or reacts in addition to a mercapto group By using a chain transfer agent (a3) having a reactive silicon group, it will have a reactive silicon group. Both methods may be used in combination.
  • a monomer (a4) 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 the (meth)acrylic acid ester (a1) groups can be introduced.
  • a chain transfer agent (a3) 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 (a1). 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 reaction method and the like 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.
  • the curable composition according to the present embodiment has a high viscosity at a relatively low temperature, but the viscosity decreases at a relatively high temperature. While the fixability to the body is good, heating to a high temperature can provide the advantage of good workability such as application to a substrate. In addition, the adhesiveness and adhesion of the curable composition to the substrate can be enhanced by blending the tackifier resin (B).
  • a general tackifying resin can be used as the tackifying resin (B).
  • terpene resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins; phenol resins, alkylphenol resins, modified phenol resins (e.g., cashew oil-modified phenol resin , tall oil-modified phenol resin, etc.), xylene-phenol resin, cyclopentadiene-phenol resin, coumarone-indene resin; gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ⁇ Rosin resins such as glycerin ester, hydrogenated rosin/glycerin ester; aromatic hydrocarbon resins such as xylene resin, low molecular weight polystyrene resin, styrene copo
  • rosin-based resins have good compatibility with the (meth)acrylic acid ester-based copolymer (A) and are excellent in the effect of achieving both improved fixability at low temperatures and improved workability by heating.
  • Terpene-based resins petroleum-based resins, alkylphenol resins, or aromatic hydrocarbon resins are preferred.
  • rosin-based resins and terpene-based resins are particularly preferred because they have a good effect of increasing stickiness and adhesiveness.
  • the rosin-based resin When using a rosin-based resin as the tackifying resin (B), the rosin-based resin preferably has an acid value of 160 KOHmg/g or less.
  • the acid value is preferably 100 mg KOH/g or less, more preferably 70 mg KOH/g or less, and even more preferably 35 mg KOH/g or less.
  • the acid value refers to the weight (mg) of potassium hydroxide required to neutralize the carboxyl groups contained in 1 g of the tackifier resin (B).
  • the amount of the tackifier resin (B) is, from the viewpoint of achieving both improvement in fixability at low temperatures and improvement in workability by heating, relative to 100 parts by weight of the (meth)acrylic acid ester copolymer (A), 1 to 100 parts by weight is preferred, 3 to 80 parts by weight is more preferred, 5 to 60 parts by weight is even more preferred, and 10 to 50 parts by weight is particularly preferred.
  • the polyoxyalkylene polymer (C) has a reactive silicon group represented by formula (1) described above.
  • the reactive silicon group of the polyoxyalkylene polymer (C) may be the same as or different from the reactive silicon group of the (meth)acrylate copolymer (A).
  • Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (C) 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; A trimethoxysilyl group is more preferred.
  • the polyoxyalkylene polymer (C) 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 (C) 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 (C) 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 (C) 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 polymer (C) may have reactive silicon groups in addition to the terminal sites, but if it has only the terminal sites, a rubber-like cured product exhibiting high elongation and low elastic modulus can be obtained. It is preferable because it becomes easy to be
  • the average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (C) 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 (C) 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 (C) may be linear or branched.
  • the number average molecular weight of the polyoxyalkylene polymer (C) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, and particularly preferably It is 3,000 or more and 30,000 or less.
  • the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (C) 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 (C) 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 (C) 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 hydrosilane compound eg, dimethoxymethylsilane, trimethoxysilane
  • a reactive silicon group-containing polyoxyalkylene polymer (C) can be obtained.
  • a polyoxyalkylene polymer (C) 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 (C) 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 (C) containing amide segments and the like may be cleaved by heat or the like.
  • a curable composition containing a polyoxyalkylene polymer (C) containing an amide segment or the like tends to have a high viscosity.
  • polyoxyalkylene polymer (C) 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 (C) 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 (C) will have a high viscosity and may be difficult to handle. There is In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (C) preferably does not contain an amide segment.
  • a method of blending a (meth)acrylic acid ester copolymer (A) and a polyoxyalkylene polymer (C) 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 (C):(A) is 95:5 to 10:90, that is, The proportion of (C) is preferably 10% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Furthermore, from the viewpoint of achieving both high strength and flexibility, (C):(A) is preferably 80:20 to 10:90, more preferably 70:30 to 20:80. The upper limit may be 50:50. Furthermore, from the viewpoint of placing emphasis on improving the final adhesive strength of the cured product, the ratio is preferably 50:50 to 10:90, more preferably 45:55 to 20:80.
  • silanol condensation catalyst is an optional component, it can promote the condensation reaction of the reactive silicon groups of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (C). , is preferably blended.
  • silanol condensation catalysts 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 used is 100 parts by weight of the (meth)acrylic acid ester copolymer (A) from the viewpoint of promoting the condensation reaction of the reactive silicon group [however, polyoxyalkylene polymer When coalescence (C) is contained, a total of 100 parts by weight of the (meth)acrylate copolymer (A) and the polyoxyalkylene polymer (C). hereinafter the same], 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 (meth)acrylate copolymer (A), a tackifier resin (B), a polyoxyalkylene polymer (C), and a silanol condensation catalyst.
  • a (meth)acrylate copolymer A
  • a tackifier resin B
  • a polyoxyalkylene polymer C
  • silanol condensation catalyst a silanol condensation catalyst.
  • plasticizers, fillers, adhesion imparting agents, dehydrating agents, rheology control agents, antioxidants, light stabilizers, ultraviolet absorbers, 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.
  • the curable composition may contain a plasticizer. By blending the plasticizer, the viscosity of the curable composition can be lowered and handling becomes easier.
  • plasticizers include, but are not limited to, dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and phthalate compounds such as butylbenzyl phthalate; (2-ethylhexyl)-1,4-benzenedicarboxylate and other terephthalic acid ester compounds; 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalic acid ester compounds; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, Aliphatic polyvalent carboxylic acid ester compounds such as diisodecyl succinate and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinole
  • Polymeric plasticizers can also be used as plasticizers.
  • 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 only one type may be used, or two or more types may be used in combination.
  • the blending amount of the plasticizer is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A). Parts by weight are particularly preferred.
  • a filler can be blended into the curable composition.
  • 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 the filler compounded is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
  • the curable composition may contain an adhesive 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 the adhesion-imparting agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
  • a dehydrating agent can be added to the curable composition.
  • 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 the dehydrating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A). 5 parts by weight is more preferred.
  • a rheology control agent may be added to the curable composition to prevent sagging and improve workability.
  • 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 content of the rheology control agent is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
  • 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 content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
  • 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 blending amount of the light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
  • 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 under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
  • the blending amount of the ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
  • 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, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
  • arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
  • 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, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
  • the curable composition according to one embodiment of the present invention can be prepared as a one-component type in which all ingredients are pre-blended and stored in a sealed container, and cured by moisture in the air after application.
  • the ingredients containing water are dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and kneading.
  • the curable composition according to one embodiment of the present invention includes a main agent containing a (meth)acrylic acid ester copolymer (A) and a tackifier resin (B), a silanol condensation catalyst, a filler, and a plasticizer. , water, etc., and can be prepared as a two-component type in which the main agent and the curing agent are mixed before use.
  • the method for preparing the curable composition according to one embodiment of the present invention is not particularly limited.
  • the above components are blended and kneaded at room temperature or under heating using a mixer, roll, kneader, etc., or a small amount of an appropriate solvent is used to dissolve and mix the above components. methods can be employed.
  • the curable composition according to one embodiment of the present invention 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 with 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 less 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 can be used as an adhesive, a sealing It can be used as a material or an adhesive.
  • the curable composition according to one embodiment of the present invention has a high viscosity at a relatively low temperature, but the viscosity can be significantly reduced at a relatively high temperature. It can be suitably used as a mold curable composition or an adhesive composition.
  • the curable composition according to one embodiment of the present invention is preferably heated to a high temperature to reduce the viscosity in order to ensure workability when applied to an adherend.
  • a high temperature about 70 to 180°C is preferable, 90 to 160°C is more preferable, and 100 to 150°C is even more preferable.
  • the heating method is not particularly limited, and conventionally known methods can be used.
  • the curable composition according to one embodiment of the present invention can express the desired physical properties by performing a long-term curing (curing) process after bonding the adherends.
  • the conditions for the curing (curing) step are not particularly limited, but include, for example, a temperature of 5 to 90° C. and a time of 24 hours to 1 week.
  • the curable composition according to one embodiment of the present invention when used as a hot-melt curable composition, it can be used as a reactive hot-melt adhesive.
  • This curable composition can be used as an adhesive for joining panels of buses, trailers, trains, etc., as an adhesive for displays and housings in smartphones, tablet terminals, laptop computers, etc.
  • -Also suitable for joining dissimilar materials such as composites and aluminum-composites.
  • a sealer it is possible to use a polymer having reactive silicon groups as shown in this application.
  • the curable composition according to one embodiment of the present invention can be It is preferably used as an adhesive used in various machine parts.
  • the curable composition according to one embodiment of the present invention when used as an adhesive composition, it can be used for general office work, paper diapers, PP film adhesion, removability, general packaging, electrical use, and fixing. Can be used for adhesive products.
  • Adhesive products containing the adhesive composition according to one embodiment of the present invention include packaging adhesive tapes, office adhesive tapes, paint masking tapes, electrical insulating adhesive tapes, binding adhesive tapes, protective adhesive tapes, identification ⁇ Decorative adhesive tapes and sheets, sports tapes, double-sided adhesive tapes, electromagnetic wave interference countermeasure films and tapes, removable films and tapes, veneer films, semiconductor chip transport tapes, marking films, protective films for deep drawing, glass scattering Prevention films, foamed adhesive tapes, waterproof/water-stopping tapes, anti-corrosion adhesive tapes, surface-protecting adhesive tapes, dicing adhesive tapes, back-grinding adhesive tapes, printing adhesive sheets, adhesive labels, and the like.
  • [Item 1] (Meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and Containing a tackifying resin (B),
  • the monomer component constituting the (meth)acrylic acid ester copolymer (A) is (meth) acrylic acid ester (a1), A polymer (a2) having more than one (meth)acryloyl group in the molecule, and containing a chain transfer agent (a3) having a mercapto group,
  • the monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon
  • a curable composition further comprising a group.
  • the tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins, terpene-based resins, petroleum-based resins, alkylphenol resins, and aromatic hydrocarbon resins. 1.
  • the polymer (a2) is a (meth)acrylate polymer (a2') having more than one (meth)acryloyl group in the molecule.
  • the curable composition according to any one of items 1 to 4 wherein the molar ratio of polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.05 or more.
  • 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)]
  • 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 (A) and the amount of the chain transfer agent (a3) having a mercapto group. be.
  • Synthesis example 1 Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal groups: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to have hydroxyl groups at both ends. , a number average molecular weight of 21,100 (termed molecular weight of terminal groups: 13,600) and a molecular weight distribution Mw/Mn of 1.21.
  • a mixed solution dissolved in .3 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 9.4 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 390 and a weight average molecular weight of 29,950 (GPC molecular weight), an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) was obtained. The solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.30 mmol/g, and a sulfur atom concentration of 4,238 ppm.
  • an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylate copolymer (A-2) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.17 mmol/g, and a sulfur atom concentration of 4,890 ppm.
  • an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-3) was obtained.
  • the solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.19 mmol/g, and a sulfur atom concentration of 5,320 ppm.
  • Example 1 YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed to 30 weight, and the isobutanol was devolatilized by heating to obtain a mixture, and the viscosity of the mixture was measured by the following method. Table 1 shows the results obtained.
  • viscosity A parallel disk plate with a diameter of 20 mm was used as a jig, the gap was set to 0.3 mm, the shear rate was set to 1 (1/sec), and the viscosity was measured while increasing the temperature from 60° C. to 150° C. at a rate of 5° C./min. . The viscosity was read at 60°C and 120°C.
  • Example 2 A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin resin, manufactured by Arakawa Chemical Industries, Ltd.) was used as the tackifier resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. bottom. Table 1 shows the results obtained.
  • Example 3 A mixture was prepared in the same manner as in Example 1 except that 50 parts by weight of FTR6125 (aromatic hydrocarbon resin, manufactured by Mitsui Chemicals, Inc.) was blended as the tackifying resin (B), and the viscosity of the mixture was measured in Example 1. was measured in the same manner as Table 1 shows the results obtained.
  • FTR6125 aromatic hydrocarbon resin, manufactured by Mitsui Chemicals, Inc.
  • Example 4 A mixture was prepared in the same manner as in Example 1 except that Nisseki Neopolymer (aromatic hydrocarbon resin, manufactured by ENEOS) was used as the tackifying resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. . Table 1 shows the results obtained.
  • Nisseki Neopolymer aromatic hydrocarbon resin, manufactured by ENEOS
  • the curable compositions of Examples 1 to 4 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 1. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). From this, it can be said that the curable compositions of Examples 1 to 4 are suitable for hot melt adhesives.
  • Example 5 YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed so as to have a weight of 60, and the isobutanol was heated and devolatilized to obtain a mixture. ) were mixed, and the viscosity of the mixture was measured by the method described above. Table 2 shows the results obtained.
  • Example 6 A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin-based resin, manufactured by Arakawa Chemical Industries, Ltd., acid value: 0) was used as the tackifier resin (B), and the viscosity of the mixture was measured in Examples. Measured in the same manner as in 5. Table 2 shows the results obtained.
  • Example 7 D-6011 (rosin-based Resin, manufactured by Arakawa Chemical Industries Co., Ltd.) was mixed to 40 weight, then isobutanol was heated and devolatilized to obtain a mixture. The viscosity of the mixture was measured in the same manner as in Example 5 after mixing N,N-diethyl-1,3-propanediamine as an amine compound. Table 2 shows the results obtained.
  • the mixture heated to 150° C. was applied to an aluminum foil having a size of 200 mm ⁇ 25 mm and a thickness of 0.1 mm so as to have a thickness of about 300 ⁇ m.
  • the coated aluminum foil was heated at 80° C. for 15 minutes to cure the mixture. After being left under conditions of 23° C. and 50% RH for 1 hour, it was attached to a stainless steel plate (100 mm ⁇ 25 mm ⁇ 1.6 mm). With the aluminum foil surface facing up, a roller of 5 kg was reciprocated 10 times to bring the aluminum foil and the stainless steel plate into close contact with each other, and allowed to stand at 23° C. and 50% RH for 24 hours.
  • a tensile test was performed so that the aluminum foil and the stainless steel plate were at 180°, and the peel strength was measured. The state of destruction was visually confirmed with CF representing cohesive failure (destruction at the adhesive portion) and AF representing interfacial failure (separation at the interface between the adhesive and the stainless steel plate).
  • the tensile test was performed using an autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 300 mm/min. Table 2 shows the results.
  • the curable compositions of Examples 5 to 7 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 2. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). In addition, it can be seen that the curable compositions of Examples 5 to 7 have higher peel strength in the peel test than Comparative Example 2. From the above, it can be said that the curable compositions of Examples 5 to 7 are suitable for adhesives.

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Abstract

This curable composition contains: (A) a (meth)acrylic acid ester-based copolymer having a reactive silicon group; and (B) a tackifying resin. Monomer components that constitute the (meth)acrylic acid ester-based copolymer (A) include: a (meth)acrylic acid ester (a1); a polymer (a2) having more than one (meth)acryloyl group in the molecule; and a chain transfer agent (a3) having a mercapto group. The monomer components further include a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group; and/or the chain transfer agent (a3), having a mercapto group, further has a reactive silicon group.

Description

硬化性組成物及びその硬化物Curable composition and cured product thereof
　本発明は、反応性ケイ素基を有する重合体を含む硬化性組成物、及びその硬化物に関する。 The present invention relates to a curable composition containing a polymer having a reactive silicon group and a cured product thereof.
　ケイ素原子上に水酸基または加水分解性基を有し、加水分解・縮合反応によってシロキサン結合を形成し得るケイ素基（以下、「反応性ケイ素基」ともいう。）を有する有機重合体は、室温でも湿分などにより反応する。かかる有機重合体が反応性ケイ素基のシロキサン縮合反応によって架橋されることで、ゴム状硬化物が得られることが知られている。 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.
　これら有機重合体の中でも、反応性ケイ素基を有するポリオキシアルキレン重合体は、比較的低粘度であることから、配合組成物を作製したり、使用する際の作業性に優れる。また、得られる硬化物の機械物性、耐候性、動的耐久性などの性能バランスがよいことから、シーリング材、接着剤、塗料などの用途に広く使用されている（特許文献１を参照）。 Among these organic polymers, 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. In addition, since 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).
　反応性ケイ素基を有するポリオキシアルキレン重合体の耐候性や接着性を改善するため、反応性ケイ素基含有ポリオキシアルキレン重合体と反応性ケイ素基含有（メタ）アクリル酸エステル系重合体を併用した硬化性組成物が知られている（特許文献２を参照）。該硬化性組成物は高耐候性シーラントや工業用接着剤として利用されている。 In order to improve the weather resistance and adhesiveness of polyoxyalkylene polymers having reactive silicon groups, a combination of reactive silicon group-containing polyoxyalkylene polymers and reactive silicon group-containing (meth)acrylic acid ester polymers was used. A curable composition is known (see Patent Document 2). The curable compositions are used as highly weather-resistant sealants and industrial adhesives.
　一方、特許文献３では、変成シリコーンやアクリル変性シリコーンを用いた一液湿気硬化型接着剤の硬化速度が遅いという欠点を解消することを目的に、硬化速度が速く、接着性にも優れた硬化性樹脂として、ポリエーテル骨格を有し両末端に二重結合を持つオリゴマーと、（メタ）アクリル酸エステル等のビニル単量体と、連鎖移動剤とをラジカル重合させて合成される反応性ケイ素基含有グラフト共重合体が記載されている。 On the other hand, in 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. A reactive silicon synthesized by radically polymerizing an oligomer having a polyether skeleton and double bonds at both ends, a vinyl monomer such as a (meth)acrylic acid ester, and a chain transfer agent as a reactive resin. Group-containing graft copolymers are described.
特開昭５２－７３９９８号公報JP-A-52-73998 特開昭５９－１２２５４１号公報JP-A-59-122541 特許第５０８２８５１号公報Japanese Patent No. 5082851
　反応性ケイ素基を有する有機重合体を含む接着剤又は粘着剤などの硬化性組成物としては、比較的低い温度領域では粘度が高く、被着体の固定性が良好である一方、高温に加熱すると粘度が低下し、基材への塗布等の作業性が良好になる物性が求められることがある。 Curable compositions such as adhesives or pressure-sensitive adhesives containing an organic polymer having a reactive silicon group have a high viscosity in a relatively low temperature range and good fixability to the adherend, while being heated to a high temperature. As a result, there is a demand for physical properties such that the viscosity decreases and workability such as application to a base material is improved.
　本発明は、上記現状に鑑み、反応性ケイ素基を有する有機重合体を含む硬化性組成物であって、比較的低温では粘度が高いにも関わらず、比較的高温になると粘度が格段に低下し得る硬化性組成物を提供することを目的とする。 In view of the above-mentioned current situation, the present invention provides a curable composition containing an organic polymer having a reactive silicon group, which has a high viscosity at a relatively low temperature, but the viscosity is significantly reduced at a relatively high temperature. An object of the present invention is to provide a curable composition capable of
　本発明者らは、上記課題を解決するために鋭意検討した結果、反応性ケイ素基含有（メタ）アクリル酸エステル系重合体を特定の単量体及び連鎖移動剤から構成し、かつ、粘着付与樹脂を併用することで、前記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a reactive silicon group-containing (meth)acrylic acid ester polymer is composed of a specific monomer and a chain transfer agent, and a tackifier The inventors have found that the above problems can be solved by using a resin together, and have completed the present invention.
　すなわち本発明は、下記一般式（１）で表される反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）、及び、粘着付与樹脂（Ｂ）を含有し、
　前記（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分が、
（メタ）アクリル酸エステル（ａ１）、
（メタ）アクリロイル基を分子内に１つより多く有する重合体（ａ２）、及び、
メルカプト基を有する連鎖移動剤（ａ３）、を含有し、
　前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）をさらに含有し、及び／又は、前記メルカプト基を有する連鎖移動剤（ａ３）が、反応性ケイ素基をさらに有する、硬化性組成物に関する。
－ＳｉＲ１ ３－ａＸａ　　　　（１）
（式中、Ｒ１は、置換又は非置換の炭素数１～２０の炭化水素基を表す。Ｘは水酸基または加水分解性基を表す。ａは２または３である。）
　また本発明は、前記硬化性組成物を硬化させて得られる硬化物に関する。 That is, the present invention contains a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and a tackifying resin (B),
The monomer component constituting the (meth)acrylic acid ester copolymer (A) is
(meth) acrylic acid ester (a1),
A polymer (a2) having more than one (meth)acryloyl group in the molecule, and
containing a chain transfer agent (a3) having a mercapto group,
The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon It relates to a curable composition further comprising groups.
—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 is 2 or 3.)
The present invention also relates to a cured product obtained by curing the curable composition.
　本発明によれば、反応性ケイ素基を有する有機重合体を含む硬化性組成物であって、比較的低温では粘度が高いにも関わらず、比較的高温になると粘度が格段に低下し得る硬化性組成物を提供することができる。
　本発明に係る硬化性組成物は、ホットメルト型硬化性組成物、又は粘着剤組成物として好適に使用することかできる。 According to the present invention, a curable composition containing an organic polymer having a reactive silicon group, which has a high viscosity at a relatively low temperature, can be cured so that the viscosity can be remarkably reduced at a relatively high temperature. A sexual composition can be provided.
The curable composition according to the present invention can be suitably used as a hot-melt curable composition or an adhesive composition.
　以下に本発明の実施形態を具体的に説明するが、本発明はこれら実施形態に限定されるものではない。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to these embodiments.
　本実施形態に係る硬化性組成物は、少なくとも、反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）、及び、粘着付与樹脂（Ｂ）を含有する。 The curable composition according to this embodiment contains at least a (meth)acrylic acid ester copolymer (A) having a reactive silicon group and a tackifying resin (B).
　＜＜反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）＞＞
　＜反応性ケイ素基＞
　（メタ）アクリル酸エステル系共重合体（Ａ）は、下記一般式（１）で表される反応性ケイ素基を分子鎖末端及び／又は側鎖（非末端部位）に有する。
－ＳｉＲ１ ３－ａＸａ　　　　（１）
（式中、Ｒ１は、置換又は非置換の炭素数１～２０の炭化水素基を表す。Ｘは水酸基または加水分解性基を表す。ａは２または３を示す。） <<(Meth)acrylic acid ester copolymer (A) having a reactive silicon group>>
<Reactive silicon group>
The (meth)acrylic ester-based copolymer (A) has a reactive silicon group represented by the following general formula (1) at the molecular chain terminal and/or side chain (non-terminal site).
—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.)
　Ｒ１の炭化水素基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましい。Ｒ１の具体例としては、例えば、メチル基、エチル基、クロロメチル基、メトキシメチル基、Ｎ，Ｎ－ジエチルアミノメチル基が挙げられる。好ましくは、メチル基、エチル基、クロロメチル基、メトキシメチル基であり、より好ましくは、メチル基、メトキシメチル基である。 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.
　Ｘとしては、例えば、ハロゲン、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などが挙げられる。これらの中では、加水分解性が穏やかで取扱いやすいことから、アルコキシ基がより好ましく、メトキシ基、エトキシ基が特に好ましい。 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. Among these, 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.
　（メタ）アクリル酸エステル系共重合体（Ａ）が有する反応性ケイ素基としては、具体的には、トリメトキシシリル基、トリエトキシシリル基、トリス（２－プロペニルオキシ）シリル基、トリアセトキシシリル基、ジメトキシメチルシリル基、ジエトキシメチルシリル基、ジメトキシエチルシリル基、（クロロメチル）ジメトキシシリル基、（クロロメチル）ジエトキシシリル基、（メトキシメチル）ジメトキシシリル基、（メトキシメチル）ジエトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジメトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジエトキシシリル基などが挙げられるが、これらに限定されない。これらの中では、メチルジメトキシシリル基、トリメトキシシリル基、トリエトキシシリル基、（クロロメチル）ジメトキシシリル基、（メトキシメチル）ジメトキシシリル基、（メトキシメチル）ジエトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジメトキシシリル基が高い活性を示し、良好な機械物性を有する硬化物が得られるため好ましく、ヤング率の高い硬化物が得られることから、トリメトキシシリル基、トリエトキシシリル基がより好ましく、トリメトキシシリル基がさらに好ましい。 Specific examples of the reactive silicon group possessed by the (meth)acrylate copolymer (A) 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. Among these are 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.
　（メタ）アクリル酸エステル系共重合体（Ａ）の反応性ケイ素基当量は特に限定はないが、０．２ｍｍｏｌ／ｇ以上が好ましく、０．５ｍｍｏｌ／ｇ以上がより好ましく、０．６ｍｍｏｌ／ｇ以上がさらに好ましい。また、前記反応性ケイ素基当量は２．０ｍｍｏｌ／ｇ以下が好ましく、硬化物の伸びの低下を抑える点から、１．０ｍｍｏｌ／ｇ以下がより好ましい。また、高剛性でかつ柔軟性の高い硬化物を得るためには、前記反応性ケイ素基当量は０．５ｍｍｏｌ／ｇ以上、１．０ｍｍｏｌ／ｇ以下が特に好ましい。 The reactive silicon group equivalent of the (meth)acrylate copolymer (A) 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. In addition, 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. Moreover, in order to obtain a highly rigid and highly flexible cured product, the reactive silicon group equivalent is particularly preferably 0.5 mmol/g or more and 1.0 mmol/g or less.
　＜単量体成分＞
　（メタ）アクリル酸エステル系共重合体（Ａ）は、少なくとも、（メタ）アクリル酸エステル（ａ１）、（メタ）アクリロイル基を分子内に１つより多く有する重合体（ａ２）、及び、メルカプト基を有する連鎖移動剤（ａ３）、を含有する単量体成分を共重合して形成される重合体である。なお、本願において「（メタ）アクリル」とは「アクリルおよび／またはメタクリル」を表す。 <Monomer component>
The (meth)acrylic acid ester-based copolymer (A) includes at least a (meth)acrylic acid ester (a1), a polymer (a2) 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 (a3) having a group. In the present application, "(meth)acryl" means "acryl and/or methacryl".
　（メタ）アクリル酸エステル系共重合体（Ａ）は、次の２つの条件のうちいずれか一方又は双方を満足することによって、反応性ケイ素基を有することになる。
条件１：前記単量体成分は、さらに、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）を含有する。
条件２：前記メルカプト基を有する連鎖移動剤（ａ３）が、反応性ケイ素基をさらに有する。
　以上のような要件を満足する反応性ケイ素基含有（メタ）アクリル酸エステル系共重合体（Ａ）を含む硬化性組成物は、比較的低温では粘度が高いにも関わらず、比較的高温になると粘度が格段に低下し得る。 The (meth)acrylic ester-based copolymer (A) has reactive silicon groups by satisfying either one or both of the following two conditions.
Condition 1: The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group.
Condition 2: The chain transfer agent (a3) having a mercapto group further has a reactive silicon group.
A curable composition containing a reactive silicon group-containing (meth)acrylic acid ester copolymer (A) that satisfies the above requirements has a high viscosity at a relatively low temperature, but can be cured at a relatively high temperature. Then the viscosity can be significantly reduced.
　高伸びの硬化物を得るためには、条件２で導入する反応性ケイ素基が条件１で導入する反応性ケイ素基よりも多いことが好ましい。具体的には、条件１で導入する反応性ケイ素基当量は、０．０１ｍｍｏｌ／ｇ以上が好ましく、０．０３ｍｍｏｌ／ｇ以上がより好ましく、０．０５ｍｍｏｌ／ｇ以上がさらに好ましい。また、条件１で導入する反応性ケイ素基当量は１．０ｍｍｏｌ／ｇ以下が好ましく、０．５ｍｍｏｌ／ｇ以下がより好ましい。一方、条件２で導入する反応性ケイ素基当量は、０．２ｍｍｏｌ／ｇ以上が好ましく、０．３ｍｍｏｌ／ｇ以上がより好ましく、０．５ｍｍｏｌ／ｇ以上がさらに好ましい。また、条件２で導入する反応性ケイ素基当量は１．５ｍｍｏｌ／ｇ以下が好ましく、１．０ｍｍｏｌ／ｇ以下がより好ましい。 In order to obtain a cured product with high elongation, it is preferable that the number of reactive silicon groups introduced under Condition 2 is greater than the number of reactive silicon groups introduced under Condition 1. Specifically, 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. Further, 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. On the other hand, 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. 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.
　高い強度を有する硬化物を得るためには、条件１及び条件２の双方により反応性ケイ素基を導入することが好ましい。具体的には、条件１で導入する反応性ケイ素基当量は、０．１ｍｍｏｌ／ｇ以上が好ましく、０．２ｍｍｏｌ／ｇ以上がより好ましく、０．３ｍｍｏｌ／ｇ以上がさらに好ましい。また、条件１で導入する反応性ケイ素基当量は１．８ｍｍｏｌ／ｇ以下が好ましく、１．０ｍｍｏｌ／ｇ以下がより好ましい。一方、条件２で導入する反応性ケイ素基当量は、０．１ｍｍｏｌ／ｇ以上が好ましく、０．２ｍｍｏｌ／ｇ以上がより好ましく、０．３ｍｍｏｌ／ｇ以上がさらに好ましい。また、条件２で導入する反応性ケイ素基当量は１．５ｍｍｏｌ／ｇ以下が好ましく、１．０ｍｍｏｌ／ｇ以下がより好ましい。 In order to obtain a cured product with high strength, it is preferable to introduce reactive silicon groups under both conditions 1 and 2. Specifically, 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. On the other hand, 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.
　＜（メタ）アクリル酸エステル（ａ１）＞
　（メタ）アクリル酸エステル（ａ１）としては特に限定されないが、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸３－メトキシブチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸のエチレンオキシド付加物、（メタ）アクリル酸２，２，２－トリフルオロエチル、（メタ）アクリル酸３，３，３－トリフルオロプロピル、（メタ）アクリル酸３，３，４，４，４－ペンタフルオロブチル、（メタ）アクリル酸２－パーフルオロエチル－２－パーフルオロブチルエチル、（メタ）アクリル酸トリフルオロメチル、（メタ）アクリル酸パーフルオロエチル、（メタ）アクリル酸ビス（トリフルオロメチル）メチル、（メタ）アクリル酸２－トリフルオロメチル－２－パーフルオロエチルエチル、（メタ）アクリル酸２－パーフルオロヘキシルエチル、（メタ）アクリル酸２－パーフルオロデシルエチル、（メタ）アクリル酸２－パーフルオロヘキサデシルエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸クロロエチル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２－アミノエチル等が挙げられる。１種類のみを使用してもよいし、２種以上を併用してもよい。
　（メタ）アクリル酸エステル（ａ１）としては（メタ）アクリル酸アルキルエステルが好ましい。 <(Meth) acrylic acid ester (a1)>
The (meth)acrylic acid ester (a1) 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)acrylic stearyl acid, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl, 2-hydroxypropyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3- (meth)acrylate trifluoropropyl, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, trifluoromethyl (meth)acrylate, Perfluoroethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexyl (meth)acrylate Ethyl, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydrofuran (meth)acrylate furyl, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate and the like. Only one type may be used, or two or more types may be used in combination.
The (meth)acrylic acid ester (a1) is preferably a (meth)acrylic acid alkyl ester.
　（メタ）アクリル酸エステル（ａ１）の含有量は、柔軟性と高剛性を両立できる観点から、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分の総量に対し３０重量％以上であることが好ましく、４０重量％以上がより好ましく、４５重量％以上が更に好ましい。上限は、８０重量％以下が好ましく、７０重量％以下がより好ましく、６５重量％以下が更に好ましい。 From the viewpoint of achieving both flexibility and high rigidity, the content of the (meth)acrylic acid ester (a1) is 30% relative to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A). 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.
　強度の高い硬化物が得られることから、（メタ）アクリル酸エステル（ａ１）としては、アルキルの炭素数が１～４である（メタ）アクリル酸アルキルエステルを含むことが好ましい。当該アルキルの炭素数が１～４である（メタ）アクリル酸アルキルエステルを、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分の総量に対し３０重量％以上含有することが好ましく、３５重量％以上がより好ましく、４０重量％以上が更に好ましい。上限は、７０重量％以下が好ましく、６０重量％以下がより好ましく、５５重量％以下が更に好ましい。 The (meth)acrylic acid ester (a1) 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 (A). 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.
　（メタ）アクリル酸エステル（ａ１）は、硬質の重合体鎖を形成して強度の高い硬化物を得ることができるため、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも１種の単量体を含有することが好ましい。特に、重合体（ａ２）を除く前記単量体成分の総量のうち、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも１種の単量体が占める割合が６０重量％以上であることが好ましく、７０重量％以上がより好ましい。 (Meth)acrylic acid ester (a1) 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 (a2), 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.
　＜（メタ）アクリロイル基を分子内に１つより多く有する重合体（ａ２）＞
　重合体（ａ２）はこれ自体が重合体であるが、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体の１つである。重合体（ａ２）は（メタ）アクリロイル基を有することによって、（メタ）アクリル酸エステル（ａ１）など他の単量体と共重合することができる。しかも、重合体（ａ２）は（メタ）アクリロイル基を１分子内に１つより多く有するため、いわゆる多官能性マクロモノマーとして機能することができる。重合体（ａ２）の主鎖骨格（後述する第二分子鎖）は、（メタ）アクリル酸エステル系共重合体（Ａ）において、主に（メタ）アクリル酸エステル（ａ１）から構成される２本の分子鎖（後述する第一分子鎖）を架橋する構造を形成し得る。以下、重合体（ａ２）を多官能性マクロモノマー（ａ２）ともいう。 <Polymer (a2) having more than one (meth)acryloyl group in the molecule>
Although the polymer (a2) is itself a polymer, it is one of the monomers constituting the (meth)acrylate copolymer (A). Since the polymer (a2) has a (meth)acryloyl group, it can be copolymerized with other monomers such as (meth)acrylic acid ester (a1). Moreover, since the polymer (a2) 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 (a2) is mainly composed of the (meth)acrylic acid ester (a1) in the (meth)acrylic acid ester-based copolymer (A) 2 It can form a structure that crosslinks the molecular chains (the first molecular chain described later). Hereinafter, the polymer (a2) is also referred to as polyfunctional macromonomer (a2).
　多官能性マクロモノマー（ａ２）が有する（メタ）アクリロイル基は、下記式（４）で表されることが好ましい。
ＣＨ２＝Ｃ（Ｒ７）－ＣＯＯ－Ｚ　　　（４）
（式中、Ｒ７は、水素またはメチル基を表す。Ｚは、多官能性マクロモノマー（ａ２）の主鎖骨格を表す。） The (meth)acryloyl group possessed by the polyfunctional macromonomer (a2) is preferably represented by the following formula (4).
CH2 =C( R7 )-COO-Z (4)
(In the formula, R 7 represents hydrogen or a methyl group. Z represents the main chain skeleton of the polyfunctional macromonomer (a2).)
　多官能性マクロモノマー（ａ２）は、（メタ）アクリロイル基を１分子内に平均して１つより多く有する。多官能性マクロモノマー（ａ２）１分子当たりの（メタ）アクリロイル基の平均個数は、１．１～５個であることが好ましく、１．３～４個がより好ましく、１．６～２．５個がさらに好ましく、１．８～２．０個が特に好ましい。尚、多官能性マクロモノマー（ａ２）は、（メタ）アクリロイル基として、アクリロイル基のみを有してもよいし、メタクリロイル基のみを有してもよいし、アクリロイル基とメタクリロイル基の双方を有してもよい。 The polyfunctional macromonomer (a2) 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 (a2) 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. As the (meth)acryloyl group, the polyfunctional macromonomer (a2) 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
　多官能性マクロモノマー（ａ２）は、（メタ）アクリロイル基を、重合体の分子鎖末端および側鎖のいずれか又は双方に有することができる。機械物性に優れる観点から、分子鎖末端に有することが好ましい。特に、多官能性マクロモノマー（ａ２）は、直鎖状の主鎖骨格を有し、その分子鎖の両末端それぞれに（メタ）アクリロイル基を有することが特に好ましい。 The polyfunctional macromonomer (a2) 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 (a2) has a linear main chain skeleton and (meth)acryloyl groups at both ends of the molecular chain.
　多官能性マクロモノマー（ａ２）の主鎖骨格は、（メタ）アクリル酸エステル系重合体であるか、又は、ポリオキシアルキレン系重合体であることが好ましい。以下では、主鎖骨格が（メタ）アクリル酸エステル系重合体である多官能性マクロモノマー（ａ２）を（ａ２′）と表記し、主鎖骨格がポリオキシアルキレン系重合体である多官能性マクロモノマー（ａ２）を（ａ２″）と表記する。 The main chain skeleton of the polyfunctional macromonomer (a2) is preferably a (meth)acrylate polymer or a polyoxyalkylene polymer. In the following, the polyfunctional macromonomer (a2) whose main chain skeleton is a (meth)acrylic acid ester polymer is denoted as (a2′), and the main chain skeleton is a polyoxyalkylene polymer. Macromonomer (a2) is denoted as (a2″).
　まず、多官能性マクロモノマー（ａ２′）について説明する。
　多官能性マクロモノマー（ａ２′）の主鎖骨格を構成する単量体としては、特に限定されず、各種（メタ）アクリル系単量体を用いることができる。（メタ）アクリル系単量体としては、例えば、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸３－メトキシブチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸のエチレンオキシド付加物、（メタ）アクリル酸２，２，２－トリフルオロエチル、（メタ）アクリル酸３，３，３－トリフルオロプロピル、（メタ）アクリル酸３，３，４，４，４－ペンタフルオロブチル、（メタ）アクリル酸２－パーフルオロエチル－２－パーフルオロブチルエチル、（メタ）アクリル酸トリフルオロメチル、（メタ）アクリル酸パーフルオロエチル、（メタ）アクリル酸ビス（トリフルオロメチル）メチル、（メタ）アクリル酸２－トリフルオロメチル－２－パーフルオロエチルエチル、（メタ）アクリル酸２－パーフルオロヘキシルエチル、（メタ）アクリル酸２－パーフルオロデシルエチル、（メタ）アクリル酸２－パーフルオロヘキサデシルエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸クロロエチル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２－アミノエチル等が挙げられる。 First, the polyfunctional macromonomer (a2') will be described.
The monomer constituting the main chain skeleton of the polyfunctional macromonomer (a2') is not particularly limited, and various (meth)acrylic monomers can be used. Examples of (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)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Stearyl acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3 (meth)acrylic acid -trifluoropropyl, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, trifluoromethyl (meth)acrylate , (meth) perfluoroethyl acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoro (meth) acrylate Hexylethyl, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydro(meth)acrylate furfuryl, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate and the like.
　更に、上記（メタ）アクリル系単量体と共重合性を示す他の単量体を併用してもよい。他の単量体としては、例えば、スチレン、ビニルトルエン、α－メチルスチレン、クロロスチレン、スチレンスルホン酸等のスチレン系単量体；パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニル単量体；マレイン酸、無水マレイン酸、マレイン酸モノアルキルエステル、マレイン酸ジアルキルエステル等のマレイン酸およびその誘導体；フマル酸、フマル酸モノアルキルエステル、フマル酸ジアルキルエステル等のフマル酸およびその誘導体；マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系単量体；酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル系単量体；エチレン、プロピレン等のオレフィン系単量体；ブタジエン、イソプレン等の共役ジエン系単量体；（メタ）アクリルアミド；（メタ）アクリロニトリル；塩化ビニル、塩化ビニリデン、塩化アリル、アリルアルコール、エチルビニルエーテル、ブチルビニルエーテル等のビニル系単量体が挙げられる。他の単量体は１種のみを使用してもよく、２種以上を併用してもよい。 Furthermore, other 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, α-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, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester monomers such as vinyl benzoate and vinyl cinnamate; olefin monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; (meth)acrylamide; (meth)acrylonitrile; Vinyl monomers such as vinyl, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether and butyl vinyl ether are included. Other monomers may be used alone or in combination of two or more.
　多官能性マクロモノマー（ａ２′）の主鎖骨格は、軟質の重合体から構成されることが好ましい。具体的には、多官能性マクロモノマー（ａ２′）の主鎖骨格を形成する単量体成分は、アクリル酸エステル（但し、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルを除く）を６０重量％以上含有することが好ましく、７０重量％以上がより好ましい。上限は、１００重量％であってもよい。 The main chain skeleton of the polyfunctional macromonomer (a2') is preferably composed of a soft polymer. Specifically, the monomer component forming the main chain skeleton of the polyfunctional macromonomer (a2′) is an acrylate ester (however, 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.
　多官能性マクロモノマー（ａ２′）を合成する方法は特に限定されないが、例えば、以下に示す方法を用いることができる。以下の方法は組み合わせて用いてもよい。
（ｉ）反応性官能基（Ｖ基）を有する単量体（例えば、アクリル酸、アクリル酸２－ヒドロキシエチル）を（メタ）アクリル系単量体と共重合した後、得られた共重合体に、Ｖ基に反応する官能基及び（メタ）アクリロイル基を有する化合物（例えば、（メタ）アクリル酸２－イソシアネートエチル）を反応させる方法。
（ｉｉ）リビングラジカル重合法によって（メタ）アクリル系単量体を重合した後、分子鎖末端（好ましくは分子鎖の両末端それぞれ）に（メタ）アクリロイル基を導入する方法。
　これらの方法のうち、分子鎖末端に（メタ）アクリロイル基を導入することができるので、（ｉｉ）の方法を用いることが好ましい。「リビングラジカル重合法」は、例えば、ジャーナル・オブ・アメリカン・ケミカル・ソサエティー（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）、１９９４年、１１６巻、７９４３頁に示されているようなコバルトポルフィリン錯体を用いるもの、特表２００３－５００３７８号公報に示されているようなニトロオキサイドラジカルを用いるもの、特開平１１－１３０９３１号公報に示されているような有機ハロゲン化物やハロゲン化スルホニル化合物などを開始剤とし、遷移金属錯体を触媒とする原子移動ラジカル重合（Ａｔｏｍ　Ｔｒａｎｓｆｅｒ　Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ：ＡＴＲＰ法）などが挙げられる。分子鎖末端に（メタ）アクリロイル基を導入しやすいことから原子移動ラジカル重合法が最も好ましい。 Although the method for synthesizing the polyfunctional macromonomer (a2') is not particularly limited, for example, the method shown below can be used. The following methods may be used in combination.
(i) a copolymer obtained by copolymerizing a monomer having a reactive functional group (V group) (e.g., acrylic acid, 2-hydroxyethyl acrylate) with a (meth)acrylic monomer; with 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).
Among these methods, it is preferable to use the method (ii) because it is possible to introduce a (meth)acryloyl group at the molecular chain terminal. The "living radical polymerization method" uses a cobalt porphyrin complex as shown, for example, in J. Am. Chem. Soc., 1994, 116, 7943. Those using nitroxide radicals as shown in JP-A-2003-500378, organic halides and sulfonyl halide compounds as shown in JP-A-11-130931 as initiators. , Atom Transfer Radical Polymerization (ATRP method) 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.
　また、特開２００１－０４００３７号公報に示されているようなメタロセン触媒と分子中に反応性ケイ素基を少なくとも１つ以上有するチオール化合物とを用いて（メタ）アクリル系重合体を得る方法を用いることも可能である。 Alternatively, a method of obtaining a (meth)acrylic polymer using a metallocene catalyst and a thiol compound having at least one reactive silicon group in the molecule as disclosed in JP-A-2001-040037 is used. is also possible.
　次に、多官能性マクロモノマー（ａ２″）について説明する。
　多官能性マクロモノマー（ａ２″）の主鎖骨格であるポリオキシアルキレン系重合体としては特に限定されず、例えば、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、ポリオキシテトラメチレン、ポリオキシエチレン－ポリオキシプロピレン共重合体、ポリオキシプロピレン－ポリオキシブチレン共重合体などが挙げられる。その中でも、ポリオキシプロピレンが好ましい。 Next, the polyfunctional macromonomer (a2″) will be explained.
The polyoxyalkylene polymer that is the main chain skeleton of the polyfunctional macromonomer (a2″) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, and polyoxyethylene. -polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Among them, polyoxypropylene is preferred.
　当該ポリオキシアルキレン系重合体の主鎖骨格は直鎖状であってもよいし、分岐状であってもよいが、直鎖状であることが好ましい。 The main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but is preferably linear.
　多官能性マクロモノマー（ａ２″）を合成する方法としては特に限定されないが、例えば、水酸基を分子内に１つより多く有するポリオキシアルキレン系重合体（好ましくは、両末端に水酸基を有する直鎖状のポリオキシアルキレン系重合体）を準備し、当該水酸基を利用して（メタ）アクリロイル基を導入する方法が挙げられる。 Although the method for synthesizing the polyfunctional macromonomer (a2″) 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.
　多官能性マクロモノマー（ａ２″）の合成法の一例として、水酸基を有するポリオキシアルキレン系重合体に対して、イソシアネート基と（メタ）アクリロイル基を有する化合物を反応させて、ウレタン結合を形成して、（メタ）アクリロイル基を導入することができる。
　前記イソシアネート基と（メタ）アクリロイル基を有する化合物の具体例としては、例えば、イソシアネートエチル（メタ）アクリレート、イソシアネートプロピル（メタ）アクリレート、イソシアネートブチル（メタ）アクリレート、イソシアネートヘキシル（メタ）アクリレート等が挙げられる。 As an example of the method for synthesizing the polyfunctional macromonomer (a2″), 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. 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.
　多官能性マクロモノマー（ａ２″）の合成法の別の例として、水酸基を有するポリオキシアルキレン系重合体に対してジイソシアネート化合物を反応させて、重合体にイソシアネート基を導入した後、水酸基と（メタ）アクリロイル基を有する化合物を反応させることで、（メタ）アクリロイル基を導入することもできる。
　前記ジイソシアネート化合物の具体例としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート等が挙げられる。
　前記水酸基と（メタ）アクリロイル基を有する化合物の具体例としては、例えば、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシエチル、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレングリコールモノ（メタ）アクリル酸エステル等が挙げられる。 As another example of the method for synthesizing the polyfunctional macromonomer (a2″), 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.
Specific examples of the diisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like.
Specific examples of 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.
　多官能性マクロモノマー（ａ２″）の合成法の更に別の例として、水酸基を有するポリオキシアルキレン系重合体に対して酸無水物を反応させて、重合体にカルボキシル基を導入した後、エポキシ基と（メタ）アクリロイル基を有する化合物を反応させることで、（メタ）アクリロイル基を導入することもできる。
　前記酸無水物の具体例としては、例えば、無水コハク酸、無水マレイン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水メチルヘキサヒドロフタル酸、無水メチルハイミック酸、無水トリメリット酸、無水メチルナジック酸、ドデシル無水コハク酸等が挙げられる。
　前記エポキシ基と（メタ）アクリロイル基を有する化合物の具体例としては、例えば、（メタ）アクリル酸グリシジル等が挙げられる。 As yet another example of a method for synthesizing the polyfunctional macromonomer (a2″), a polyoxyalkylene polymer having a hydroxyl group is reacted with an acid anhydride 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.
Specific examples of the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl anhydride. Himic acid, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride and the like.
Specific examples of the compound having an epoxy group and a (meth)acryloyl group include glycidyl (meth)acrylate.
　多官能性マクロモノマー（ａ２″）の合成法の更に別の例として、水酸基を有するポリオキシアルキレン系重合体に対して、メタクリル酸、アクリル酸を脱水縮合させる方法がある。また、反応をより温和な条件で実施するためには、水酸基を有するポリオキシアルキレン系重合体に対して、メタクリル酸クロリド、メタクリル酸ブロミド、メタクリル酸ヨージド、アクリル酸クロリド、アクリル酸ブロミド、アクリル酸ヨージドなどを反応させる方法がある。 Still another example of the method for synthesizing the polyfunctional macromonomer (a2″) is a method of dehydration condensation of methacrylic acid and acrylic acid on a polyoxyalkylene polymer having a hydroxyl group. In order to carry out under mild conditions, 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.
　多官能性マクロモノマー（ａ２）の数平均分子量は特に限定されないが、硬化物が発揮する機械物性及び接着性と、（ａ２）の取り扱いの容易さを両立する観点から、５００以上が好ましく、１，０００以上がより好ましく、２，０００以上がさらに好ましい。また、１００，０００以下が好ましく、５０，０００以下がより好ましく、４０，０００以下がさらに好ましく、３０，０００以下が特に好ましい。 The number average molecular weight of the polyfunctional macromonomer (a2) 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 (a2). ,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.
　多官能性マクロモノマー（ａ２）の重量平均分子量は特に限定されないが、硬化物が発揮する機械物性及び接着性と、（ａ２）の取り扱いの容易さを両立する観点から、５００以上が好ましく、１，０００以上が好ましく、２，５００以上がさらに好ましい。また、１３０，０００以下が好ましく、６５，０００以下がより好ましく、６０，０００以下がさらに好ましく、３０，０００以下がより更に好ましい。 The weight average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably 500 or more from the viewpoint of achieving both the mechanical properties and adhesive properties exhibited by the cured product and the ease of handling of (a2). ,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.
　多官能性マクロモノマー（ａ２）の分子量分布（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））は特に限定されないが、狭いことが好ましく、具体的には２．０未満が好ましく、１．６以下がより好ましく、１．５以下がさらに好ましく、１．４以下がより更に好ましく、１．３以下が特に好ましく、１．２以下が最も好ましい。 The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polyfunctional macromonomer (a2) 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.
　多官能性マクロモノマー（ａ２）の数平均分子量（Ｍｎ）および重量平均分子量（Ｍｗ）は、ＧＰＣ（ポリスチレン換算）により測定される値であり、その詳しい測定法は実施例で記載する。 The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyfunctional macromonomer (a2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.
　（メタ）アクリル酸エステル系共重合体（Ａ）は、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖と、多官能性マクロモノマー（ａ２）の主鎖骨格に由来する分子鎖を有する。多官能性マクロモノマー（ａ２）は重合性基である（メタ）アクリロイル基を１分子内に１つより多く有するため、（メタ）アクリル酸エステル系共重合体（Ａ）は、多官能性マクロモノマー（ａ２）の主鎖骨格に由来する分子鎖１本に対して、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖が１本より多く結合した構造を有し得る。多官能性マクロモノマー（ａ２）の主鎖骨格に由来する分子鎖は、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖の末端又は側鎖（非末端部位）のいずれに導入されていてもよいが、接着性の観点から、側鎖に導入されていることが好ましい。 The (meth)acrylic acid ester-based copolymer (A) has a molecular chain mainly composed of the (meth)acrylic acid ester (a1) and a molecule derived from the main chain skeleton of the polyfunctional macromonomer (a2). have chains. Since the polyfunctional macromonomer (a2) has more than one (meth)acryloyl group in one molecule, which is a polymerizable group, the (meth)acrylic acid ester copolymer (A) is a polyfunctional macro It may have a structure in which more than one molecular chain mainly composed of the (meth)acrylic acid ester (a1) is bonded to one molecular chain derived from the main chain skeleton of the monomer (a2). The molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) 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 (a1). However, from the viewpoint of adhesiveness, it is preferably introduced into the side chain.
　特に、多官能性マクロモノマー（ａ２）が主鎖骨格の両末端それぞれに（メタ）アクリロイル基を有する場合、多官能性マクロモノマー（ａ２）の主鎖骨格に由来する分子鎖の両末端それぞれに、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖が結合したＨ型構造が形成され得る。ここで、多官能性マクロモノマー（ａ２）の主鎖骨格に由来する分子鎖がＨの横棒に相当し、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖が、Ｈに含まれる２本の縦棒に相当する。Ｈ型構造については後述する。 In particular, when the polyfunctional macromonomer (a2) has a (meth)acryloyl group at each of both ends of the main chain skeleton, each of both ends of the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) , an H-type structure can be formed in which molecular chains composed mainly of (meth)acrylic acid ester (a1) are bonded. Here, the molecular chain derived from the main chain skeleton of the polyfunctional macromonomer (a2) corresponds to the horizontal bar of H, and the molecular chain mainly composed of the (meth)acrylic acid ester (a1) Corresponds to the two vertical bars included. The H-shaped structure will be described later.
　多官能性マクロモノマー（ａ２）の含有量は、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分の総量に対し１重量％以上７０重量％以下であることが好ましく、５重量％以上６０重量％以下がより好ましく、１０重量％以上５０重量％以下がさらにより好ましく、１５重量％以上４５重量％以下が特に好ましい。なかでも、ヤング率の高い硬化物を得る場合には、多官能性マクロモノマー（ａ２）の含有量は、３５重量％未満が好ましい。一方、ヤング率の低い硬化物を得る場合には、多官能性マクロモノマー（ａ２）の含有量は、３５重量％以上が好ましい。 The content of the polyfunctional macromonomer (a2) 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 (A). , 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. Above all, when obtaining a cured product with a high Young's modulus, the content of the polyfunctional macromonomer (a2) is preferably less than 35% by weight. On the other hand, when obtaining a cured product with a low Young's modulus, the content of the polyfunctional macromonomer (a2) is preferably 35% by weight or more.
　また、多官能性マクロモノマー（ａ２）の含有量は、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分中、０．０５モル％以上６．０モル％以下を占めることが好ましく、０．１モル％以上２．３モル％以下を占めることがより好ましく、０．２モル％以上１．５モル％以下を占めることがさらに好ましい。以上の範囲では、（メタ）アクリル酸エステル系共重合体（Ａ）を合成する時のゲル化を抑制しつつ、多官能性マクロモノマー（ａ２）の使用による効果を達成することができる。 In addition, the content of the polyfunctional macromonomer (a2) is 0.05 mol% or more and 6.0 mol% or less in the monomer components constituting the (meth)acrylate copolymer (A). 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 effect of using the polyfunctional macromonomer (a2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylate copolymer (A).
　（メタ）アクリル酸エステル系共重合体（Ａ）１分子当たりの多官能性マクロモノマー（ａ２）の平均個数は、得られる硬化物の強度の観点から、０．０５以上２．０以下であることが好ましい。下限は、０．０７以上がより好ましく、０．０８以上がさらに好ましい。上限は、１．５以下がより好ましく、１．０以下がさらに好ましい。前記平均個数は、次の式で算出することができる。
式：（メタ）アクリル酸エステル系共重合体（Ａ）の数平均分子量（ｇ／ｍｏｌ）／（（メタ）アクリル酸エステル系共重合体（Ａ）の重量（ｇ）／（多官能性マクロモノマー（ａ２）のモル数）） The average number of polyfunctional macromonomers (a2) per molecule of (meth)acrylic acid ester copolymer (A) 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.
Formula: Number average molecular weight (g / mol) of (meth) acrylic ester copolymer (A) / ((meth) acrylic ester copolymer (A) weight (g) / (polyfunctional macro Number of moles of monomer (a2)))
　＜メルカプト基を有する連鎖移動剤（ａ３）＞
　（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分に、メルカプト基を有する連鎖移動剤（ａ３）を含めることによって、多官能性マクロモノマー（ａ２）を使用しているにも関わらず、（メタ）アクリル酸エステル系共重合体（Ａ）の分子量分布を比較的狭くし、かつ（メタ）アクリル酸エステル系共重合体（Ａ）を合成する時のゲル化を抑制することができる。また、（メタ）アクリル酸エステル系共重合体（Ａ）の１分子に多官能性マクロモノマー（ａ２）が１分子導入された重合体分子を優先的に合成することが可能となる。 <Chain transfer agent (a3) having a mercapto group>
A polyfunctional macromonomer (a2) is used by including a chain transfer agent (a3) having a mercapto group in the monomer component constituting the (meth)acrylate copolymer (A). Nevertheless, the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is relatively narrowed, and gelation is suppressed when synthesizing the (meth)acrylic acid ester copolymer (A). can do. In addition, it becomes possible to preferentially synthesize a polymer molecule in which one molecule of the polyfunctional macromonomer (a2) is introduced into one molecule of the (meth)acrylate copolymer (A).
　メルカプト基を有する連鎖移動剤（ａ３）は、反応性ケイ素基を有しないものであってもよいが、反応性ケイ素基をさらに有することが好ましい。当該反応性ケイ素基は、前述した式（１）で表される反応性ケイ素基である。メルカプト基を有する連鎖移動剤（ａ３）が反応性ケイ素基を有することによって、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖の末端に反応性ケイ素基を導入することができる。 The chain transfer agent (a3) 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. When the chain transfer agent (a3) having a mercapto group has a reactive silicon group, a reactive silicon group can be introduced at the end of the molecular chain mainly composed of the (meth)acrylic acid ester (a1). .
　メルカプト基を有する連鎖移動剤（ａ３）としては特に限定されないが、例えば、３－メルカプトプロピルジメトキシメチルシラン、３－メルカプトプロピルトリメトキシシラン、（メルカプトメチル）ジメトキシメチルシラン、（メルカプトメチル）トリメトキシシラン、ｎ－ドデシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ラウリルメルカプタン等が挙げられる。 Although the chain transfer agent (a3) 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.
　メルカプト基を有する連鎖移動剤（ａ３）の含有量は、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分の総量に対し１重量％以上１５重量％以下であることが好ましく、２重量％以上１０重量％以下がより好ましく、３重量％以上８重量％以下がより好ましい。 The content of the chain transfer agent (a3) 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 (A). 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.
　また、メルカプト基を有する連鎖移動剤（ａ３）の含有量は、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分中０．１モル％以上２０モル％以下を占めることが好ましく、０．４モル％以上１５モル％以下を占めることがより好ましく、０．５モル％以上１０モル％以下を占めることがさらに好ましく、０．６モル％以上８モル％以下を占めることが特に好ましい。以上の範囲では、メルカプト基を有する連鎖移動剤（ａ３）を使用することによる効果を達成できる。 In addition, the content of the chain transfer agent (a3) 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 (A). 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 (a3) having a mercapto group can be achieved.
　多官能性マクロモノマー（ａ２）の含有量とメルカプト基を有する連鎖移動剤（ａ３）の含有量は、得られる硬化物の強度が向上するため、多官能性マクロモノマー（ａ２）／メルカプト基を有する連鎖移動剤（ａ３）のモル比は、０．０３以上が好ましく、０．０５以上がより好ましく、０．０９以上がさらに好ましく、０．１以上が特に好ましい。前記モル比の上限は特に限定されないが、１以下が好ましく、０．５以下がより好ましく、０．３以下がさらに好ましい。 The content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent (a3) having a mercapto group improve the strength of the resulting cured product, so that the polyfunctional macromonomer (a2)/mercapto group The molar ratio of the chain transfer agent (a3) 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. Although 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.
　（メタ）アクリル酸エステル系共重合体（Ａ）は、メルカプト基を有する連鎖移動剤（ａ３）に由来する置換基（後述する－Ｓ－Ｒ８で表される構造）を有し得るものであるため、硫黄原子を含み得る。（メタ）アクリル酸エステル系共重合体（Ａ）中の硫黄原子濃度は７００ｐｐｍ以上２０，０００ｐｐｍ以下であることが好ましく、１，０００ｐｐｍ以上１５，０００ｐｐｍ以下がより好ましい。 The (meth)acrylic acid ester copolymer (A) may have a substituent derived from the chain transfer agent (a3) having a mercapto group (structure represented by -SR 8 described later). Therefore, it may contain sulfur atoms. The sulfur atom concentration in the (meth)acrylate copolymer (A) 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.
　硫黄原子濃度の測定方法は特に限定されない。有機元素分析、蛍光Ｘ線分析など、既知の元素分析方法により測定することができる。また、硫黄原子濃度は、（メタ）アクリル酸エステル系共重合体（Ａ）の製造に使用した単量体成分の合計量と、メルカプト基を有する連鎖移動剤の量（ａ３）から算出される理論値であってもよい。 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 (A) and the amount (a3) of the chain transfer agent having a mercapto group. It may be a theoretical value.
　＜反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）＞
　反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）は、任意の単量体であり、使用しなくともよいが、使用することが好ましい。単量体（ａ４）が有する反応性ケイ素基は、前述した式（１）で表される反応性ケイ素基である。単量体（ａ４）を使用することによって、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖の側鎖（非末端部位）に反応性ケイ素基を導入することができる。 <Monomer (a4) having a reactive silicon group and a polymerizable unsaturated group>
The monomer (a4) 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 (a4) is the reactive silicon group represented by formula (1) described above. By using the monomer (a4), a reactive silicon group can be introduced into the side chain (non-terminal portion) of the molecular chain mainly composed of the (meth)acrylic acid ester (a1).
　反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）としては、例えば、３－（メタ）アクリロキシプロピルトリメトキシシラン、３－（メタ）アクリロキシプロピルトリエトキシシラン、３－（メタ）アクリロキシプロピルジメトキシメチルシラン、（メタ）アクリロキシメチルトリメトキシシラン、（メタ）アクリロキシメチルジメトキシメチルシランなどの（メタ）アクリロキシ基と反応性ケイ素基を有する化合物；ビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニル基と反応性ケイ素基を有する化合物等が挙げられる。これら化合物は１種のみを使用してもよく、２種以上を併用してもよい。 Examples of the monomer (a4) 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.
　単量体（ａ４）を使用する場合、単量体（ａ４）の含有量は、（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分の総量に対し０．１重量％以上５０重量％以下であることが好ましく、０．５重量％以上３０重量％以下がより好ましく、１重量％以上２０重量％以下がさらに好ましく、２重量％以上１５重量％以下が特に好ましい。また、硬化性組成物のチキソ性向上、及び、高伸びの硬化物が得られる観点から、単量体（ａ４）の含有量は、１０重量％以下であることが好ましい。 When using the monomer (a4), the content of the monomer (a4) is 0.1 weight with respect to the total amount of the monomer components constituting the (meth)acrylic acid ester copolymer (A) % 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 (a4) 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.
　＜他の単量体（ｂ５）＞
　（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分は、以上で詳述した（ａ１）～（ａ４）のいずれにも該当しない他の単量体（ｂ５）を含有するものであってもよいし、含有しないものであってもよい。
　他の単量体（ｂ５）としては、（メタ）アクリル酸エステル（ａ１）や反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）に該当しない（メタ）アクリル系単量体や、該（メタ）アクリル系単量体以外の単量体が挙げられる。具体的には、多官能性マクロモノマー（ａ２′）について上述した他の単量体を使用することができる。 <Other monomer (b5)>
The monomer component constituting the (meth)acrylic acid ester-based copolymer (A) contains another monomer (b5) that does not correspond to any of (a1) to (a4) detailed above. It may contain, or may not contain.
Other monomers (b5) include (meth)acrylic esters (a1) and monomers (a4) 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 (a2') can be used.
　＜（メタ）アクリル酸エステル系共重合体（Ａ）の分子量＞
　（メタ）アクリル酸エステル系共重合体（Ａ）の数平均分子量は特に限定されないが、ＧＰＣ測定によるポリスチレン換算分子量で、５００以上５０，０００以下であることが好ましく、５００以上３０，０００以下がより好ましく、１，０００以上１０，０００以下が特に好ましい。なかでも、低粘度の（メタ）アクリル酸エステル系共重合体（Ａ）が得られることから、数平均分子量は７，０００以下が好ましい。また、低粘度で良好な接着性が発揮され得ることから、数平均分子量は３，５００以下であることが好ましい。 <Molecular weight of (meth)acrylate copolymer (A)>
The number average molecular weight of the (meth)acrylic acid ester copolymer (A) 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)acrylate copolymer (A) 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.
　（メタ）アクリル酸エステル系共重合体（Ａ）の重量平均分子量は特に限定されないが、ＧＰＣ測定によるポリスチレン換算分子量で、５００以上８０，０００以下であることが好ましく、３，０００以上７０，０００以下がより好ましく、５，０００以上６５，０００以下が特に好ましい。なかでも、低粘度で強度の高い硬化物が得られることから、重量平均分子量は２０，０００以下であることが好ましい。 The weight average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 or more and 80,000 or less, and 3,000 or more and 70,000. 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.
　（メタ）アクリル酸エステル系共重合体（Ａ）の重量平均分子量と、多官能性マクロモノマー（ａ２）の重量平均分子量に関しては、次の式で算出される値が１．１以上であることが好ましい。
式：（共重合体（Ａ）の重量平均分子量）／（多官能性マクロモノマー（ａ２）の重量平均分子量）
　前記式で算出される値が１．１以上であるということは、（メタ）アクリル酸エステル系共重合体（Ａ）１分子中の多官能性マクロモノマー（ａ２）の平均導入個数が多いことを意味しており、得られる硬化物の強度がより向上し得る。
　硬化物の強度の観点から、前記式で算出される値は、１．１以上であることが好ましく、１．２以上がより好ましく、１．３以上がさらに好ましい。上限は特に限定されないが、１０以下が好ましく、５以下がより好ましい。 Regarding the weight average molecular weight of the (meth)acrylate copolymer (A) and the weight average molecular weight of the polyfunctional macromonomer (a2), the value calculated by the following formula is 1.1 or more. is preferred.
Formula: (weight average molecular weight of copolymer (A))/(weight average molecular weight of polyfunctional macromonomer (a2))
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 (a2) in one molecule of the (meth)acrylic acid ester copolymer (A) is large. It means that the strength of the resulting cured product can be further improved.
From the viewpoint of the strength of the cured product, 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. Although the upper limit is not particularly limited, it is preferably 10 or less, more preferably 5 or less.
　（メタ）アクリル酸エステル系共重合体（Ａ）の分子量分布は特に限定されないが、（メタ）アクリル酸エステル系共重合体（Ａ）を低粘度とする観点から、３．０以上１１．０以下が好ましく、３．２以上１０．０以下がより好ましく、３．４以上８．０以下がさらに好ましい。（メタ）アクリル酸エステル系共重合体（Ａ）の分子量分布は、ＧＰＣ測定により得られる数平均分子量と重量平均分子量から求めることが出来る。 The molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (A) low in viscosity, it is 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 (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
　＜（メタ）アクリル酸エステル系共重合体（Ａ）の構造＞
　好適な態様によると、（メタ）アクリル酸エステル系共重合体（Ａ）は、トリブロック共重合体を含み得る。該トリブロック共重合体は、２つの第一分子鎖が、１つの第二分子鎖を介して結合している構造を含む。第一分子鎖は、主に（メタ）アクリル酸エステル（ａ１）が重合してなる分子鎖から構成され、第二分子鎖は、多官能性マクロモノマー（ａ２）の主鎖骨格から構成される。 <Structure of (meth)acrylate copolymer (A)>
According to a preferred embodiment, the (meth)acrylate copolymer (A) 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 (a1), and the second molecular chain is composed of the main chain skeleton of the polyfunctional macromonomer (a2). .
　第一分子鎖は、（ａ１）、（ａ２）中の（メタ）アクリロイル基、（ａ３）、任意の（ａ４）、及び任意の他の単量体の共重合によって形成される分子鎖である。この第一分子鎖に反応性ケイ素基が結合している。メルカプト基を有する連鎖移動剤（ａ３）が反応性ケイ素基を有する場合、第一分子鎖の末端に反応性ケイ素基が結合し、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）を使用する場合、第一分子鎖の非末端部位に反応性ケイ素基が結合している。
　一方、第二分子鎖は、多官能性マクロモノマー（ａ２）中の（メタ）アクリル酸エステル系重合体またはポリオキシアルキレン系重合体の主鎖骨格にあたる。 The first molecular chain is a molecular chain formed by copolymerization of (a1), (meth)acryloyl groups in (a2), (a3), optional (a4), and optional other monomers. . A reactive silicon group is attached to this first molecular chain. When the chain transfer agent (a3) having a mercapto group has a reactive silicon group, a reactive silicon group is bonded to the end of the first molecular chain, and a monomer having a reactive silicon group and a polymerizable unsaturated group ( When a4) is used, a reactive silicon group is attached to the non-terminal portion of the first molecular chain.
On the other hand, the second molecular chain corresponds to the main chain skeleton of the (meth)acrylate polymer or polyoxyalkylene polymer in the polyfunctional macromonomer (a2).
　２つの第一分子鎖と１つの第二分子鎖の結合方式は、通常のＡＢＡ型のトリブロック共重合体とは異なり、第二分子鎖の両末端がそれぞれ、第一分子鎖の非末端部位に結合している形式である。即ち、該トリブロック共重合体は、Ｈ型の構造を含み、この時、Ｈ中の２本の縦棒が２つの第一分子鎖にあたり、Ｈ中の１本の横棒が１つの第二分子鎖にあたる。 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. is a form that is bound to That is, 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.
　但し、（メタ）アクリル酸エステル系共重合体（Ａ）は、Ｈ型構造のトリブロック共重合体に限定されるものではなく、Ｈ型構造のトリブロック共重合体に加えて、他の構造を有するブロック共重合体を含有していてもよい。そのような他の構造を有するブロック共重合体としては、例えば、３つの第一分子鎖が、２つの第二分子鎖を介して結合している構造を有するブロック共重合体などが挙げられる。 However, the (meth)acrylic acid ester-based copolymer (A) 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.
　第一分子鎖と第二分子鎖は、多官能性マクロモノマー（ａ２）中の（メタ）アクリロイル基に由来するエステル結合（即ち、前記式（４）中のエステル結合に対応するエステル結合）を介して結合している。 The first molecular chain and the second molecular chain have an ester bond derived from the (meth)acryloyl group in the polyfunctional macromonomer (a2) (that is, an ester bond corresponding to the ester bond in the formula (4)). are connected through
　前記第一分子鎖が硬質の重合体から構成され、前記第二分子鎖が軟質の重合体から構成される場合、高強度で高伸びの硬化物が得られることから好ましい。ここで、硬質の重合体とは、ガラス転移温度が高い重合体を指す。軟質の重合体とは、ガラス転移温度が低い重合体を指す。 When 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. Here, 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.
　第一分子鎖が硬質の重合体から構成される場合、第一分子鎖を構成する単量体成分（即ち、多官能性マクロモノマー（ａ２）を除く単量体成分）は、メタクリル酸エステル、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルからなる群より選択される少なくとも１種の単量体を含有することが好ましい。第一分子鎖を構成する単量体成分の総量のうち前記単量体が占める割合は６０重量％以上であることが好ましく、７０重量％以上がより好ましい。上限は１００重量％であってもよい。 When the first molecular chain is composed of a rigid polymer, the monomer components constituting the first molecular chain (that is, the monomer components excluding the polyfunctional macromonomer (a2)) 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.
　また、第二分子鎖が軟質の重合体から構成される場合、第二分子鎖は、ポリオキシアルキレン系重合体の主鎖骨格であってもよいし、（メタ）アクリル酸エステル系重合体であってもよい。但し、後者の場合、第二分子鎖を構成する単量体成分（（ａ２′）の主鎖骨格を形成する単量体成分）は、アクリル酸エステル（但し、アクリル酸イソボルニル、アクリル酸ジシクロペンテニル、及び、アクリル酸ジシクロペンタニルを除く）を含有することが好ましい。第二分子鎖を構成する単量体成分のうち前記アクリル酸エステルが占める割合は６０重量％以上であることが好ましく、７０重量％以上がより好ましい。上限は１００重量％であってもよい。 In addition, 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. There may be. However, in the latter case, the monomer component constituting the second molecular chain (the monomer component forming the main chain skeleton of (a2′)) 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.
　前記第一分子鎖はメルカプト基を有する連鎖移動剤（ａ３）を反応させて形成される分子鎖であるため、前記第一分子鎖のいずれかの末端に、（ａ３）に由来する置換基として、－Ｓ－Ｒ８で表される構造を有し得る。前記式中、Ｓは硫黄原子を表し、Ｒ８は、反応性ケイ素基を有していてもよい炭化水素基を表す。前記炭化水素基とは、炭素数１～２０のアルキル基、アリール基、又はアラルキル基等が挙げられる。前記反応性ケイ素基は、前述した式（１）で表される反応性ケイ素基である。Ｒ８の具体例としては、例えば、反応性ケイ素基含有メチル基、反応性ケイ素基含有プロピル基、ｎ－ドデシル基、ｔｅｒｔ－ドデシル基、ラウリル基等が挙げられる。 Since the first molecular chain is a molecular chain formed by reacting the chain transfer agent (a3) having a mercapto group, at either end of the first molecular chain, as a substituent derived from (a3) , —SR 8 . In the above formula, S represents a sulfur atom and 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.
　上述した多官能性マクロモノマー（ａ２）／メルカプト基を有する連鎖移動剤（ａ３）のモル比に対応して、得られる硬化物の強度向上の観点から、（メタ）アクリル酸エステル系共重合体（Ａ）において、前記－Ｓ－Ｒ８に対する、多官能性マクロモノマー（ａ２）の主鎖骨格のモル比は、０．０３以上であることが好ましく、０．０５以上がより好ましく、０．０９以上がさらに好ましく、０．１以上が特に好ましい。前記モル比の上限は特に限定されないが、１以下が好ましく、０．５以下がより好ましく、０．３以下がさらに好ましい。 Corresponding to the molar ratio of the polyfunctional macromonomer (a2) / chain transfer agent (a3) having a mercapto group, from the viewpoint of improving the strength of the resulting cured product, a (meth) acrylic acid ester copolymer In (A), the molar ratio of the main chain skeleton of the polyfunctional macromonomer (a2) 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. Although 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.
　＜（メタ）アクリル酸エステル系共重合体（Ａ）の製造方法＞
　（メタ）アクリル酸エステル系共重合体（Ａ）は、前記単量体成分を重合することによって製造できる。その重合方法は特に限定されないが、一般的なフリーラジカル重合であってよい。本実施形態によると、フリーラジカル重合であるにも関わらず、重合の制御が可能で、ブロック共重合体である（メタ）アクリル酸エステル系共重合体（Ａ）を製造することができ、しかも、その分子量分布を比較的狭くすることができる。 <Method for producing (meth)acrylate copolymer (A)>
The (meth)acrylate copolymer (A) 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, the polymerization can be controlled, and the (meth)acrylic acid ester copolymer (A), which is a block copolymer, can be produced. , its molecular weight distribution can be relatively narrow.
　前記フリーラジカル重合で使用可能な重合開始剤としては、例えば、２，２’－アゾビス（２－メチルブチロニトリル）、ジメチル２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス［Ｎ－（２－プロペニル）－２－メチルプロピオンアミド］、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）などのアゾ系化合物；ベンゾイルパーオキサイド、イソブチリルパーオキサイド、イソノナノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキシドなどのジアシルパーオキサイド；ジイソプロピルパージカーボネート、ジ－ｓｅｃ－ブチルパージカーボネート、ジ－２－エチルヘキシルパージカーボネート、ジ－１－メチルヘプチルパージカーボネート、ジ－３－メトキシブチルパージカーボネート、ジシクロヘキシルパージカーボネートなどのパーオキシジカーボネート；ｔｅｒｔ－ブチルパーベンゾエート、ｔｅｒｔ－ブチルパーアセテート、ｔｅｒｔ－ブチルパー－２－エチルへキサノエート、ｔｅｒｔ－ブチルパーイソブチレート、ｔｅｒｔ－ブチルパーピバレート、ｔｅｒｔ－ブチルジパーアジペート、キュミルパーネオデカノエートなどのパーオキシエステル；メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイドなどのケトンパーオキサイド；ジ－ｔｅｒｔ－ブチルパーオキサイド、ジキュミルパーオキサイド、ｔｅｒｔ－ブチルキュミルパーオキサイド、１，１－ジ（ｔｅｒｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサンなどのジアルキルパーオキサイド；キュメンヒドロキシパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイドなどのハイドロパーオキサイド；１，１－ジ（ｔｅｒｔ－ヘキシルパーオキシ）－３，３，５－トリメチルシクロヘキサンなどの過酸化物などが挙げられる。これら重合開始剤は１種のみで使用してもよく、２種以上を併用しても良い。 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-ethylhexyl purge carbonate, di-1-methylheptyl Peroxydicarbonates such as purged carbonate, di-3-methoxybutyl purged carbonate, dicyclohexyl purged carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyl Peroxyesters such as lactate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, dialkyl peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; cumene hydroxyl peroxide, tert-butyl hydro hydroperoxides such as peroxides; peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; These polymerization initiators may be used alone or in combination of two or more.
　前記フリーラジカル重合で使用可能な溶媒としては、例えば、トルエン、キシレン、スチレン、エチルベンゼン、パラジクロルベンゼン、フタル酸ジ－２－エチルヘキシル、フタル酸ジ－ｎ－ブチルなどの芳香族系溶剤；ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素系溶剤；酢酸ブチル、酢酸ｎ－プロプル、酢酸イソプロピルなどのカルボン酸エステル化合物；メチルイソブチルケトン、メチルエチルケトンなどのケトン化合物；ジメチルカーボネート、ジエチルカーボネートなどのジアルキルカーボネート化合物；ｎ－プロパノール、２－プロパノール、ｎ－ブタノール、２－ブタノール、イソブタノール、ｔｅｒｔ－ブタノール、アミルアルコールなどのアルコール化合物などが挙げられる。なかでも、分子量分布が狭くなることからアルコール化合物が好ましい。溶解力が高いことから芳香族系溶剤が好ましい。臭気が低いことから脂肪族炭化水素系溶剤が好ましい。（メタ）アクリル酸エステル系共重合体（Ａ）の分子量分布は連鎖移動剤（ａ３）の添加量と溶媒に影響を受ける。連鎖移動剤（ａ３）の添加量が３重量％以下である場合には溶媒の種類に大きく影響を受ける。分子量分布の狭い（メタ）アクリル酸エステル系共重合体（Ａ）を得たい場合には、溶媒としてイソブタノールを用いることが好ましい。 Examples of 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. 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 (A) is affected by the amount of the chain transfer agent (a3) added and the solvent. When the amount of chain transfer agent (a3) added is 3% by weight or less, it is greatly affected by the type of solvent. When it is desired to obtain a (meth)acrylate copolymer (A) with a narrow molecular weight distribution, isobutanol is preferably used as the solvent.
　上述の通り、（メタ）アクリル酸エステル系共重合体（Ａ）は、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）を使用するか、又は、メルカプト基に加えて反応性ケイ素基を有する連鎖移動剤（ａ３）を使用することによって、反応性ケイ素基を有することになる。両方法は併用してもよい。反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）を使用することによって、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖の側鎖にランダムに反応性ケイ素基を導入することができる。また、メルカプト基に加えて反応性ケイ素基を有する連鎖移動剤（ａ３）を使用することによって、主に（メタ）アクリル酸エステル（ａ１）から構成される分子鎖の末端に反応性ケイ素基を導入することができる。 As described above, the (meth)acrylic acid ester copolymer (A) uses a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, or reacts in addition to a mercapto group By using a chain transfer agent (a3) having a reactive silicon group, it will have a reactive silicon group. Both methods may be used in combination. By using a monomer (a4) 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 the (meth)acrylic acid ester (a1) groups can be introduced. Further, by using a chain transfer agent (a3) 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 (a1). can be introduced.
　しかし、（メタ）アクリル酸エステル系共重合体（Ａ）に反応性ケイ素基をさらに導入するため、以下の方法を併用することもできる。
（ｉｉｉ）反応性官能基（Ｖ基）を有する単量体を（メタ）アクリル酸エステル（ａ１）などと共重合した後、得られた共重合体に、Ｖ基に反応する官能基と反応性ケイ素基を有する化合物を反応させる方法。具体的には、アクリル酸２－ヒドロキシエチルを共重合した後、反応性ケイ素基を有するイソシアネートシラン化合物を反応させる方法や、アクリル酸グリシジルを共重合した後、反応性ケイ素基を有するアミノシラン化合物を反応させる方法などが例示できる。
（ｉｖ）リビングラジカル重合法によって合成した（メタ）アクリル酸エステル系共重合体の末端官能基を変性して、反応性ケイ素基を導入する方法。リビングラジカル重合法によって得られる（メタ）アクリル酸エステル系共重合体は重合体末端に官能基を導入しやすく、これを変性することで重合体末端に反応性ケイ素基を導入することができる。 However, in order to further introduce a reactive silicon group into the (meth)acrylic acid ester copolymer (A), the following methods can be used in combination.
(iii) After copolymerizing a monomer having a reactive functional group (V group) with a (meth)acrylic acid ester (a1) or the like, the resulting copolymer is reacted with a functional group that reacts with the V group. a method of reacting a compound having a silicon group. Specifically, after copolymerizing 2-hydroxyethyl acrylate, 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 reaction method and the like can be exemplified.
(iv) A method of modifying terminal functional groups of a (meth)acrylic acid ester-based copolymer synthesized by a living radical polymerization method to introduce a reactive silicon group. 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.
　方法（ｉｉｉ）で使用するＶ基に反応する官能基と反応性ケイ素基を有する化合物としては、例えば、３－イソシアネートプロピルジメトキシメチルシラン、３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、イソシアネートメチルジメトキシメチルシラン、イソシアネートメチルトリメトキシシラン、イソシアネートメチルトリエトキシシランなどのイソシアネートシラン化合物；３－グリシドキシプロピルジメトキシメチルシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、グリシドキシメチルジメトキシメチルシラン、グリシドキシメチルトリメトキシシラン、グリシドキシメチルトリエトキシシランなどのエポキシシラン化合物；３－アミノプロピルジメトキシメチルシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、アミノメチルジメトキシメチルシラン、アミノメチルトリメトキシシラン、アミノメチルトリエトキシシラン、Ｎ－シクロヘキシルアミノメチルジメトキシメチルシラン、Ｎ－シクロヘキシルアミノメチルトリメトキシシラン、Ｎ－シクロヘキシルアミノメチルトリエトキシシランなどのアミノシラン化合物などが挙げられる。 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. , isocyanatomethyldimethoxymethylsilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane; 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Epoxysilane compounds such as triethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane; 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3 -aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane Examples include aminosilane compounds such as silane.
　方法（ｉｖ）では、任意の変性反応を利用できるが、例えば、リビングラジカル重合によって得られた末端官能基に反応し得る反応性基と反応性ケイ素基を有する化合物を用いる方法や、末端官能基に反応し得る反応性基と二重結合を有する化合物を用いて重合体末端に二重結合を導入した後、ヒドロシリル化反応等を利用して反応性ケイ素基を導入する方法などが挙げられる。 In method (iv), any modification reaction can be used. A method of introducing a double bond at the end of a polymer using a compound having a reactive group capable of reacting with a double bond and then introducing a reactive silicon group using a hydrosilylation reaction or the like.
　＜＜粘着付与樹脂（Ｂ）＞＞
　本実施形態に係る硬化性組成物は、粘着付与樹脂（Ｂ）を含有することにより、比較的低温では粘度が高いにも関わらず、比較的高温では粘度が低下することから、低温では被着体の固定性が良好である一方、高温に加熱すると基材への塗布等の作業性が良好になる利点を得ることができる。また、粘着付与樹脂（Ｂ）の配合によって、基材への硬化性組成物の接着性や密着性を高めることもできる。 <<Tackifier resin (B)>>
By containing the tackifying resin (B), the curable composition according to the present embodiment has a high viscosity at a relatively low temperature, but the viscosity decreases at a relatively high temperature. While the fixability to the body is good, heating to a high temperature can provide the advantage of good workability such as application to a substrate. In addition, the adhesiveness and adhesion of the curable composition to the substrate can be enhanced by blending the tackifier resin (B).
　粘着付与樹脂（Ｂ）としては、一般的な粘着付与樹脂を使用することができる。具体例としては特に限定されないが、テルペン樹脂、芳香族変性テルペン樹脂、水素添加テルペン樹脂、テルペン－フェノール樹脂等のテルペン系樹脂；フェノール樹脂、アルキルフェノール樹脂、変性フェノール樹脂（例えば、カシューオイル変性フェノール樹脂、トール油変性フェノール樹脂等）、キシレン－フェノール樹脂、シクロペンタジエン－フェノール樹脂、クマロンインデン樹脂；ガムロジン、トール油ロジン、ウッドロジン、水添ロジン、不均化ロジン、重合ロジン、マレイン化ロジン、ロジン・グリセリンエステル、水添ロジン・グリセリンエステル等のロジン系樹脂；キシレン樹脂、低分子量ポリスチレン系樹脂、スチレン共重合体樹脂、スチレン系ブロック共重合体及びその水素添加物などの芳香族系炭化水素樹脂；石油樹脂（例えば、Ｃ５炭化水素樹脂、Ｃ９炭化水素樹脂、Ｃ５Ｃ９炭化水素共重合樹脂等）、水添石油樹脂等の石油系樹脂；ＤＣＰＤ樹脂等が挙げられる。粘着付与樹脂（Ｂ）としては１種類のみを使用してもよいし、２種類以上を併用してもよい。 A general tackifying resin can be used as the tackifying resin (B). Specific examples are not particularly limited, but terpene resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins; phenol resins, alkylphenol resins, modified phenol resins (e.g., cashew oil-modified phenol resin , tall oil-modified phenol resin, etc.), xylene-phenol resin, cyclopentadiene-phenol resin, coumarone-indene resin; gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin・Rosin resins such as glycerin ester, hydrogenated rosin/glycerin ester; aromatic hydrocarbon resins such as xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, styrene block copolymer and hydrogenated products thereof petroleum-based resins such as petroleum resins (eg, C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.) and hydrogenated petroleum resins; and DCPD resins. As the tackifying resin (B), only one type may be used, or two or more types may be used in combination.
　なかでも、（メタ）アクリル酸エステル系共重合体（Ａ）との相溶性が良好で、低温での固定性の向上と加熱による作業性改善を両立する効果に優れる点から、ロジン系樹脂、テルペン系樹脂、石油系樹脂、アルキルフェノール樹脂、又は、芳香族系炭化水素樹脂が好ましい。さらに、粘着性と接着性を高める効果が良好であることから、ロジン系樹脂、テルペン系樹脂が特に好ましい。 Among them, rosin-based resins have good compatibility with the (meth)acrylic acid ester-based copolymer (A) and are excellent in the effect of achieving both improved fixability at low temperatures and improved workability by heating. Terpene-based resins, petroleum-based resins, alkylphenol resins, or aromatic hydrocarbon resins are preferred. Furthermore, rosin-based resins and terpene-based resins are particularly preferred because they have a good effect of increasing stickiness and adhesiveness.
　粘着付与樹脂（Ｂ）としてロジン系樹脂を使用する場合、該ロジン系樹脂は、酸価が１６０ＫＯＨｍｇ／ｇ以下を示すことが好ましい。酸価が１６０ＫＯＨｍｇ／ｇ以下のロジン系樹脂を使用することで、硬化性組成物を加熱した時のゲル化を抑制することができる。前記酸価は、１００ＫＯＨｍｇ／ｇ以下であることが好ましく、７０ＫＯＨｍｇ／ｇ以下がより好ましく、３５ＫＯＨｍｇ／ｇ以下がさらに好ましい。前記酸価は、粘着付与樹脂（Ｂ）１ｇ中に含まれるカルボキシル基を中和するのに必要な水酸化カリウムの重量（ｍｇ）を指す。 When using a rosin-based resin as the tackifying resin (B), the rosin-based resin preferably has an acid value of 160 KOHmg/g or less. By using a rosin-based resin having an acid value of 160 KOHmg/g or less, it is possible to suppress gelation when the curable composition is heated. The acid value is preferably 100 mg KOH/g or less, more preferably 70 mg KOH/g or less, and even more preferably 35 mg KOH/g or less. The acid value refers to the weight (mg) of potassium hydroxide required to neutralize the carboxyl groups contained in 1 g of the tackifier resin (B).
　粘着付与樹脂（Ｂ）の配合量は、低温での固定性の向上と加熱による作業性改善を両立する観点から、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、１～１００重量部が好ましく、３～８０重量部がより好ましく、５～６０重量部がさらに好ましく、１０～５０重量部が特に好ましい。 The amount of the tackifier resin (B) is, from the viewpoint of achieving both improvement in fixability at low temperatures and improvement in workability by heating, relative to 100 parts by weight of the (meth)acrylic acid ester copolymer (A), 1 to 100 parts by weight is preferred, 3 to 80 parts by weight is more preferred, 5 to 60 parts by weight is even more preferred, and 10 to 50 parts by weight is particularly preferred.
　＜＜反応性ケイ素基を有するポリオキシアルキレン系重合体（Ｃ）＞＞
　本発明の一実施形態に係る硬化性組成物は、前述した反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）に加えて、反応性ケイ素基を有するポリオキシアルキレン系重合体（Ｃ）（以下、単に「ポリオキシアルキレン系重合体（Ｃ）」ともいう）を含有してもよい。 <<Polyoxyalkylene Polymer (C) Having Reactive Silicon Group>>
The curable composition according to one embodiment of the present invention, in addition to the (meth) acrylic acid ester copolymer (A) having a reactive silicon group described above, a polyoxyalkylene polymer having a reactive silicon group Coalesced (C) (hereinafter also simply referred to as "polyoxyalkylene polymer (C)") may be contained.
　＜反応性ケイ素基＞
　ポリオキシアルキレン系重合体（Ｃ）は、前述した式（１）で表される反応性ケイ素基を有する。ポリオキシアルキレン系重合体（Ｃ）が有する反応性ケイ素基は、（メタ）アクリル酸エステル系共重合体（Ａ）が有する反応性ケイ素基と同一であってよいし、異なっていてもよい。 <Reactive silicon group>
The polyoxyalkylene polymer (C) has a reactive silicon group represented by formula (1) described above. The reactive silicon group of the polyoxyalkylene polymer (C) may be the same as or different from the reactive silicon group of the (meth)acrylate copolymer (A).
　ポリオキシアルキレン系重合体（Ｃ）が有する反応性ケイ素基としては、具体的には、トリメトキシシリル基、トリエトキシシリル基、トリス（２－プロペニルオキシ）シリル基、トリアセトキシシリル基、ジメトキシメチルシリル基、ジエトキシメチルシリル基、ジメトキシエチルシリル基、（クロロメチル）ジメトキシシリル基、（クロロメチル）ジエトキシシリル基、（メトキシメチル）ジメトキシシリル基、（メトキシメチル）ジエトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジメトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジエトキシシリル基などが挙げられるが、これらに限定されない。これらの中では、メチルジメトキシシリル基、トリメトキシシリル基、トリエトキシシリル基、（クロロメチル）ジメトキシシリル基、（メトキシメチル）ジメトキシシリル基、（メトキシメチル）ジエトキシシリル基、（Ｎ，Ｎ－ジエチルアミノメチル）ジメトキシシリル基が高い活性を示し、良好な機械物性を有する硬化物が得られるため好ましく、高強度の硬化物が得られることから、トリメトキシシリル基、トリエトキシシリル基がより好ましく、トリメトキシシリル基がさらに好ましい。 Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (C) 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. Among these are 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; A trimethoxysilyl group is more preferred.
　ポリオキシアルキレン系重合体（Ｃ）は、１つの末端部位に平均して１個以下の反応性ケイ素基を有するものであってもよいし、１つの末端部位に平均して１個より多い反応性ケイ素基を有するものであってもよい。ここで、１つの末端部位に平均して１個より多い反応性ケイ素基を有するとは、ポリオキシアルキレン系重合体（Ｃ）に、１つの末端部位に２個以上の反応性ケイ素基を有するポリオキシアルキレンが含まれていることを示している。 The polyoxyalkylene polymer (C) 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. Here, having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (C) has two or more reactive silicon groups at one terminal site. It shows that polyoxyalkylene is included.
　２個以上の反応性ケイ素基を有する末端部位は、例えば、下記一般式（２）で表すことができる。 A terminal site having two or more reactive silicon groups can be represented, for example, by the following general formula (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ２，Ｒ４はそれぞれ独立に２価の炭素数１～６の結合基を表し、Ｒ２，Ｒ４に隣接するそれぞれの炭素原子と結合する原子は、炭素、酸素、窒素のいずれかである。Ｒ３，Ｒ５はそれぞれ独立に、水素、または炭素数１～１０の炭化水素基を表す。ｎは１～１０の整数である。Ｒ１、Ｘ、ａは前記式（１）について上述のとおりである。） (In the formula, 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.)
　Ｒ２、Ｒ４としては、２価の炭素数１～６の有機基であってよく、酸素原子を含んでもよい炭化水素基であってもよい。該炭化水素基の炭素数は１～４が好ましく、１～３がより好ましく、１～２がさらに好ましい。Ｒ２の具体例としては、例えば、－ＣＨ２ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＨ２－が挙げられるが、好ましくは、－ＣＨ２ＯＣＨ２－である。Ｒ４の具体例としては、例えば、－ＣＨ２－、－ＣＨ２ＣＨ２－が挙げられるが、好ましくは、－ＣＨ２－である。 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 -. Specific examples of R 4 include -CH 2 - and -CH 2 CH 2 -, preferably -CH 2 -.
　Ｒ３、Ｒ５の炭化水素基の炭素数としては１～５が好ましく、１～３がより好ましく、１～２がさらに好ましい。Ｒ３、Ｒ５の具体例としては、例えば、水素原子、メチル基、エチル基が挙げられるが、好ましくは、水素原子、メチル基であり、より好ましくは水素原子である。 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.
　一般式（２）で表される末端部位は、特に好ましい態様によると、Ｒ２が－ＣＨ２ＯＣＨ２－であり、Ｒ４が－ＣＨ２－であり、Ｒ３及びＲ５がそれぞれ水素原子である。ｎは１～５の整数が好ましく、１～３の整数がより好ましく、１又は２がさらに好ましい。ただし、ｎは、１つの値に限定されるものではなく、複数の値が混在していてもよい。 According to a particularly preferred embodiment, 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. is. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2. However, n is not limited to one value, and may be a mixture of multiple values.
　ポリオキシアルキレン系重合体（Ｃ）は、反応性ケイ素基を、１つの末端部位に平均して１．０個以下有するものであってもよい。この場合、前記平均数は、０．４個以上であることが好ましく、０．５個以上がより好ましく、０．６個以上がさらに好ましい。 The polyoxyalkylene polymer (C) may have an average of 1.0 or less reactive silicon groups at one terminal site. In this case, the average number is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more.
　また、ポリオキシアルキレン系重合体（Ｃ）は、反応性ケイ素基を、１つの末端部位に平均して１．０個より多く有するものであってもよい。この場合、前記平均数は、１．１個以上であることがより好ましく、１．５個以上が更に好ましく、２．０個以上がより更に好ましい。また、前記平均数は、５個以下であることが好ましく、３個以下がより好ましい。 In addition, the polyoxyalkylene polymer (C) may have an average of more than 1.0 reactive silicon groups at one terminal site. In this case, 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. Moreover, the average number is preferably 5 or less, more preferably 3 or less.
　ポリオキシアルキレン系重合体（Ｃ）は、末端部位以外に反応性ケイ素基を有しても良いが、末端部位にのみ有することが、高伸びで、低弾性率を示すゴム状硬化物が得られやすくなるため好ましい。 The polyoxyalkylene polymer (C) may have reactive silicon groups in addition to the terminal sites, but if it has only the terminal sites, a rubber-like cured product exhibiting high elongation and low elastic modulus can be obtained. It is preferable because it becomes easy to be
　ポリオキシアルキレン系重合体（Ｃ）が有する反応性ケイ素基の１分子当たりの平均個数は、硬化物の強度の観点から、１．０個より多いことが好ましく、１．２個以上がより好ましく、１．３個以上がさらに好ましく、１．５個以上がより更に好ましく、１．７個以上が特に好ましい。前記平均個数は、２．０個以下であってもよいし、２．０個より多くてもよい。硬化物の伸びの観点から、６．０個以下が好ましく、５．５個以下がより好ましく、５．０個以下が最も好ましい。 The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (C) 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.
　＜主鎖構造＞
　ポリオキシアルキレン系重合体（Ｃ）の主鎖骨格には特に制限はなく、例えば、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、ポリオキシテトラメチレン、ポリオキシエチレン－ポリオキシプロピレン共重合体、ポリオキシプロピレン－ポリオキシブチレン共重合体などが挙げられる。その中でも、ポリオキシプロピレンが好ましい。 <Main chain structure>
The main chain skeleton of the polyoxyalkylene polymer (C) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, Examples include polyoxypropylene-polyoxybutylene copolymers. Among them, polyoxypropylene is preferred.
　ポリオキシアルキレン系重合体（Ｃ）の主鎖構造は直鎖状であってもよいし、分岐状であってもよい。 The main chain structure of the polyoxyalkylene polymer (C) may be linear or branched.
　ポリオキシアルキレン系重合体（Ｃ）の数平均分子量は、ＧＰＣにおけるポリスチレン換算分子量において、好ましくは３，０００以上１００，０００以下、より好ましくは３，０００以上５０，０００以下であり、特に好ましくは３，０００以上３０，０００以下である。 The number average molecular weight of the polyoxyalkylene polymer (C) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, and particularly preferably It is 3,000 or more and 30,000 or less.
　ポリオキシアルキレン系重合体（Ｃ）の分子量分布（Ｍｗ／Ｍｎ）は特に限定されないが、狭いことが好ましく、具体的には、２．０未満が好ましく、１．６以下がより好ましく、１．５以下がさらに好ましく、１．４以下が特に好ましい。また、硬化物の耐久性や伸びを向上させる等、各種機械的物性を向上させる観点からは、１．２以下が好ましい。ポリオキシアルキレン系重合体（Ｃ）の分子量分布は、ＧＰＣ測定により得られる数平均分子量と重量平均分子量から求めることができる。 Although the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (C) 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 (C) can be obtained from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
　＜ポリオキシアルキレン系重合体（Ｃ）の合成方法＞
　ポリオキシアルキレン系重合体（Ｃ）の合成方法は特に限定されない。一例を説明すると、まず、水酸基を有する開始剤にエポキシ化合物を重合させて水酸基末端重合体を得る。該重合体の水酸基にアルカリ金属塩（例えばナトリウムメトキシド）を作用させた後、炭素－炭素不飽和結合を有するハロゲン化炭化水素化合物（例えば塩化アリル）を反応させて、重合体末端に炭素－炭素不飽和結合を導入する。次いで、反応性ケイ素基含有ヒドロシラン化合物（例えば、ジメトキメチルシラン、トリメトキシシラン）を反応させることで、反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｃ）を得ることができる。 <Method for synthesizing polyoxyalkylene polymer (C)>
The method for synthesizing the polyoxyalkylene polymer (C) is not particularly limited. To explain an example, first, an initiator having a hydroxyl group is polymerized with an epoxy compound to obtain a hydroxyl group-terminated polymer. After reacting the hydroxyl groups of the polymer with an alkali metal salt (for example, sodium methoxide), a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond (for example, allyl chloride) is reacted to attach a carbon- Introduce carbon unsaturated bonds. Then, by reacting a reactive silicon group-containing hydrosilane compound (eg, dimethoxymethylsilane, trimethoxysilane), a reactive silicon group-containing polyoxyalkylene polymer (C) can be obtained.
　好適な一実施形態である１つの末端部位に平均して１．０個より多い反応性ケイ素基を有しているポリオキシアルキレン系重合体（Ｃ）は次のようにして得ることができる。上記と同様に前記水酸基末端重合体の水酸基に前記アルカリ金属塩を作用させた後、まず炭素－炭素不飽和結合を有するエポキシ化合物（例えば、アリルグリシジルエーテル）を反応させ、次いで前記炭素－炭素不飽和結合を有するハロゲン化炭化水素化合物（例えば塩化アリル）を反応させることで、１つの末端に２個以上の炭素－炭素不飽和結合を導入する。その後、反応性ケイ素基含有ヒドロシラン化合物を反応させればよい。 A polyoxyalkylene polymer (C) 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.
　また、前記反応性ケイ素基含有ヒドロシラン化合物の代わりに、反応性ケイ素基含有メルカプトシラン類を用いることで、重合体に反応性ケイ素基を導入することも可能である。 It is also possible to introduce a reactive silicon group into the polymer by using a reactive silicon group-containing mercaptosilane instead of the reactive silicon group-containing hydrosilane compound.
　ポリオキシアルキレン系重合体（Ｃ）の主鎖は、エステル結合、または、一般式（３）：
－ＮＲ６－Ｃ（＝Ｏ）－　　（３）
（式中、Ｒ６は炭素数１～１０の有機基または水素原子を表す）で表されるアミドセグメントを含んでいてもよい。 The main chain of the polyoxyalkylene polymer (C) is an ester bond or the general formula (3):
-NR 6 -C(=O)- (3)
(wherein R 6 represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).
　エステル結合またはアミドセグメントを含有するポリオキシアルキレン系重合体（Ｃ）を含む硬化性組成物から得られる硬化物は、水素結合の作用等により、高い硬度および強度を有する場合がある。しかし、アミドセグメント等を含有するポリオキシアルキレン系重合体（Ｃ）は、熱等により開裂する可能性がある。また、アミドセグメント等を含有するポリオキシアルキレン系重合体（Ｃ）を含む硬化性組成物は、粘度が高くなる傾向がある。以上のようなメリットおよびデメリットを考慮して、ポリオキシアルキレン系重合体（Ｃ）として、アミドセグメント等を含有するポリオキシアルキレンを使用してもよく、アミドセグメント等を含有しないポリオキシアルキレンを使用してもよい。 A cured product obtained from a curable composition containing a polyoxyalkylene polymer (C) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds and the like. However, the polyoxyalkylene polymer (C) containing amide segments and the like may be cleaved by heat or the like. Moreover, a curable composition containing a polyoxyalkylene polymer (C) containing an amide segment or the like tends to have a high viscosity. Considering the above merits and demerits, as the polyoxyalkylene polymer (C), 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
　前記一般式（３）で表されるアミドセグメントとしては、例えば、イソシアネート基と水酸基との反応、アミノ基とカーボネートとの反応、イソシアネート基とアミノ基との反応、イソシアネート基とメルカプト基との反応等により形成されるものが挙げられる。また、活性水素原子を含む前記アミドセグメントとイソシアネート基との反応により形成されるものも、一般式（３）で表されるアミドセグメントに含まれる。 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.
　アミドセグメントを含有するポリオキシアルキレン系重合体（Ｃ）の製造方法の一例としては、末端に活性水素含有基を有するポリオキシアルキレンに、ポリイソシアネート化合物を反応させて、末端にイソシアネート基を有する重合体を合成した後、またはその合成と同時に、該イソシアネート基と反応し得る官能基（例えば、水酸基、カルボキシ基、メルカプト基、１級アミノ基または２級アミノ基）と反応性ケイ素基を併せ持つ化合物を反応させる方法が挙げられる。また、別の例として、末端に活性水素含有基を有するポリオキシアルキレンに、反応性ケイ素基含有イソシアネート化合物を反応させる方法が挙げられる。 As an example of a method for producing the polyoxyalkylene polymer (C) containing an amide segment, 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) capable of reacting with the isocyanate group and a reactive silicon group after or simultaneously with the synthesis of the coalescence. 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.
　ポリオキシアルキレン系重合体（Ｃ）がアミドセグメントを含む場合、ポリオキシアルキレン系重合体（Ｃ）１分子あたりのアミドセグメントの数（平均値）は、１～１０が好ましく、１．５～５がより好ましく、２～３が特に好ましい。この数が１よりも少ない場合には、硬化性が十分ではない場合があり、逆に１０よりも大きい場合には、ポリオキシアルキレン系重合体（Ｃ）が高粘度となり、取り扱い難くなる可能性がある。硬化性組成物の粘度を低くし、作業性を改善するためには、ポリオキシアルキレン系重合体（Ｃ）は、アミドセグメントを含まないことが好ましい。 When the polyoxyalkylene polymer (C) contains amide segments, the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (C) 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 (C) will have a high viscosity and may be difficult to handle. There is In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (C) preferably does not contain an amide segment.
　（メタ）アクリル酸エステル系共重合体（Ａ）とポリオキシアルキレン系重合体（Ｃ）をブレンドする方法は、特開昭５９－１２２５４１号公報、特開昭６３－１１２６４２号公報、特開平６－１７２６３１号公報、特開平１１－１１６７６３号公報等に提案されている。他にも、反応性ケイ素基を有するポリオキシプロピレン系重合体の存在下で（メタ）アクリル酸エステル系単量体の重合を行う方法が利用できる。 A method of blending a (meth)acrylic acid ester copolymer (A) and a polyoxyalkylene polymer (C) 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. Alternatively, 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.
　ポリオキシアルキレン系重合体（Ｃ）と（メタ）アクリル酸エステル系共重合体（Ａ）を併用する場合、重量比（Ｃ）：（Ａ）は９５：５～１０：９０であること、即ち（Ｃ）の割合が１０重量％以上９５重量％以下であることが好ましい。この範囲内であると、柔軟性と高いせん断接着強度を示す硬化物を得ることができる。さらに、高強度と柔軟性を両立する点で、（Ｃ）：（Ａ）は８０：２０～１０：９０であることが好ましく、７０：３０～２０：８０であることがより好ましい。上限は、５０：５０であってもよい。さらに、硬化物の最終的な接着強度向上を重視する観点からは、５０：５０～１０：９０であることが好ましく、４５：５５～２０：８０であることがより好ましい。 When the polyoxyalkylene polymer (C) and the (meth)acrylate copolymer (A) are used in combination, the weight ratio (C):(A) is 95:5 to 10:90, that is, The proportion of (C) is preferably 10% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Furthermore, from the viewpoint of achieving both high strength and flexibility, (C):(A) is preferably 80:20 to 10:90, more preferably 70:30 to 20:80. The upper limit may be 50:50. Furthermore, from the viewpoint of placing emphasis on improving the final adhesive strength of the cured product, the ratio is preferably 50:50 to 10:90, more preferably 45:55 to 20:80.
　＜＜シラノール縮合触媒＞＞
　シラノール縮合触媒は、任意の成分であるが、（メタ）アクリル酸エステル系共重合体（Ａ）およびポリオキシアルキレン系重合体（Ｃ）の反応性ケイ素基の縮合反応を促進することができるため、配合されることが好ましい。 <<Silanol condensation catalyst>>
Although the silanol condensation catalyst is an optional component, it can promote the condensation reaction of the reactive silicon groups of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (C). , is preferably blended.
　シラノール縮合触媒としては、例えば、有機錫化合物、カルボン酸金属塩、アミン化合物、カルボン酸、アルコキシ金属などが挙げられる。 Examples of silanol condensation catalysts include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
　有機錫化合物の具体例としては、ジブチル錫ジラウレート、ジブチル錫ジオクタノエート、ジブチル錫ビス（ブチルマレエート）、ジブチル錫ジアセテート、ジブチル錫オキサイド、ジブチル錫ビス（アセチルアセトナート）、ジブチル錫オキサイドとシリケート化合物との反応物、ジブチル錫オキサイドとフタル酸エステルとの反応物、ジオクチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ビス（エチルマレエート）、ジオクチル錫ビス（オクチルマレエート）、ジオクチル錫ビス（アセチルアセトナート）、ジオクチル錫ジステアレート、ジオクチル錫オキサイド、ジオクチル錫オキサイドとシリケート化合物との反応物などが挙げられる。 Specific examples of 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.
　カルボン酸金属塩の具体例としては、カルボン酸錫、カルボン酸ビスマス、カルボン酸チタン、カルボン酸ジルコニウム、カルボン酸鉄、カルボン酸カリウム、カルボン酸カルシウムなどが挙げられる。カルボン酸金属塩としては下記のカルボン酸と各種金属を組み合わせることができる。 Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As the carboxylic acid metal salt, the following carboxylic acid and various metals can be combined.
　アミン化合物の具体例としては、オクチルアミン、２－エチルヘキシルアミン、ラウリルアミン、ステアリルアミンなどのアミン類；ピリジン、１，８－ジアザビシクロ［５，４，０］ウンデセン－７（ＤＢＵ）、１，５－ジアザビシクロ［４，３，０］ノネン－５（ＤＢＮ）などの含窒素複素環式化合物；グアニジン、フェニルグアニジン、ジフェニルグアニジンなどのグアニジン類；ブチルビグアニド、１－ｏ－トリルビグアニドや１－フェニルビグアニドなどのビグアニド類；アミノ基含有シランカップリング剤；ケチミン化合物などが挙げられる。 Specific examples of 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.
　カルボン酸の具体例としては、酢酸、プロピオン酸、酪酸、２－エチルヘキサン酸、ラウリン酸、ステアリン酸、オレイン酸、リノール酸、ネオデカン酸、バーサチック酸などが挙げられる。 Specific examples of 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.
　アルコキシ金属の具体例としては、テトラブチルチタネート、チタンテトラキス（アセチルアセトナート）、ジイソプロポキシチタンビス（エチルアセトセテート）などのチタン化合物や、アルミニウムトリス（アセチルアセトナート）、ジイソプロポキシアルミニウムエチルアセトアセテートなどのアルミニウム化合物、ジルコニウムテトラキス（アセチルアセトナート）などのジルコニウム化合物などが挙げられる。 Specific examples of alkoxy metals include 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.
　その他のシラノール縮合触媒として、フッ素アニオン含有化合物、光酸発生剤や光塩基発生剤も使用できる。 As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
　シラノール縮合触媒は、異なる２種類以上の触媒を併用して使用してもよく、例えば、前記のアミン化合物とカルボン酸や、アミン化合物とアルコキシ金属を併用することで、反応性が向上する効果が得られる可能性がある。 The silanol condensation catalyst may be used in combination of two or more different catalysts. For example, 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.
　シラノール縮合触媒を使用する場合、その使用量としては、反応性ケイ素基の縮合反応促進の観点から、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部［但し、ポリオキシアルキレン系重合体（Ｃ）を含有する場合、（メタ）アクリル酸エステル系共重合体（Ａ）とポリオキシアルキレン系重合体（Ｃ）の合計１００重量部。以下同様］に対して、０．００１～２０重量部であることが好ましく、０．０１～１５重量部がより好ましく、０．０１～１０重量部がさらに好ましい。 When using a silanol condensation catalyst, the amount used is 100 parts by weight of the (meth)acrylic acid ester copolymer (A) from the viewpoint of promoting the condensation reaction of the reactive silicon group [however, polyoxyalkylene polymer When coalescence (C) is contained, a total of 100 parts by weight of the (meth)acrylate copolymer (A) and the polyoxyalkylene polymer (C). hereinafter the same], 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.
　＜＜その他の添加剤＞＞
　本実施形態に係る硬化性組成物には、（メタ）アクリル酸エステル系共重合体（Ａ）、粘着付与樹脂（Ｂ）、ポリオキシアルキレン系重合体（Ｃ）、及びシラノール縮合触媒の他に、添加剤として、可塑剤、充填剤、接着性付与剤、脱水剤、レオロジーコントロール剤、酸化防止剤、光安定剤、紫外線吸収剤、その他の樹脂を添加しても良い。 <<Other Additives>>
The curable composition according to the present embodiment includes a (meth)acrylate copolymer (A), a tackifier resin (B), a polyoxyalkylene polymer (C), and a silanol condensation catalyst. As additives, plasticizers, fillers, adhesion imparting agents, dehydrating agents, rheology control agents, antioxidants, light stabilizers, ultraviolet absorbers, and other resins may be added.
　また、本実施形態に係る硬化性組成物には、硬化性組成物又は硬化物の諸物性の調整を目的として、必要に応じて各種添加剤を添加してもよい。このような添加物の例としては、たとえば、溶剤、希釈剤、光硬化性物質、酸素硬化性物質、表面性改良剤、シリケート、硬化性調整剤、ラジカル禁止剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、防かび剤、難燃剤、発泡剤などが挙げられる。 In addition, various 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. Examples of such 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.
　＜可塑剤＞
　硬化性組成物には、可塑剤を配合することができる。可塑剤の配合によって、硬化性組成物を低粘度化することができ、取り扱いが容易になる。 <Plasticizer>
The curable composition may contain a plasticizer. By blending the plasticizer, the viscosity of the curable composition can be lowered and handling becomes easier.
　可塑剤としては特に限定されないが、例えば、ジブチルフタレート、ジイソノニルフタレート（ＤＩＮＰ）、ジヘプチルフタレート、ジ（２－エチルヘキシル）フタレート、ジイソデシルフタレート（ＤＩＤＰ）、およびブチルベンジルフタレートなどのフタル酸エステル化合物；ビス（２－エチルヘキシル）－１，４－ベンゼンジカルボキシレートなどのテレフタル酸エステル化合物；１，２－シクロヘキサンジカルボン酸ジイソノニルエステルなどの非フタル酸エステル化合物；アジピン酸ジオクチル、セバシン酸ジオクチル、セバシン酸ジブチル、コハク酸ジイソデシル、およびアセチルクエン酸トリブチルなどの脂肪族多価カルボン酸エステル化合物；オレイン酸ブチル、およびアセチルリシノール酸メチルなどの不飽和脂肪酸エステル化合物；リン酸エステル化合物；トリメリット酸エステル化合物；塩素化パラフィン；アルキルジフェニル、および部分水添ターフェニルなどの炭化水素系油；プロセスオイル；エポキシ化大豆油、エポキシ化アマニ油、ビス（２－エチルヘキシル）－４，５－エポキシシクロヘキサン－１，２－ジカーボキシレート（Ｅ－ＰＳ）、エポキシオクチルステアレート、エポキシブチルステアレートおよびエポキシステアリン酸ベンジルなどのエポキシ可塑剤；アルキルスルホン酸エステルなどが挙げられる。 Examples of plasticizers include, but are not limited to, dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and phthalate compounds such as butylbenzyl phthalate; (2-ethylhexyl)-1,4-benzenedicarboxylate and other terephthalic acid ester compounds; 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalic acid ester compounds; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, Aliphatic polyvalent carboxylic acid ester compounds such as diisodecyl succinate and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phosphate ester compounds; trimellitate ester compounds; paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-di Epoxy plasticizers such as carboxylate (E-PS), epoxyoctyl stearate, epoxybutylstearate and epoxybenzyl stearate; alkyl sulfonate esters, and the like.
　可塑剤として、高分子可塑剤を使用することもできる。高分子可塑剤の具体例としては、ビニル系重合体；ポリエステル系可塑剤；数平均分子量５００以上のポリエチレングリコール、ポリプロピレングリコールなどのポリエーテルポリオール、これらポリエーテルポリオールのヒドロキシ基をエステル基、エーテル基などに変換した誘導体などのポリエーテル系可塑剤；ポリスチレン類；ポリブタジエン、ポリブテン、ポリイソブチレン、ブタジエン－アクリロニトリル、ポリクロロプレン等が挙げられる。
　中でも、高分子可塑剤が好ましく、ポリエーテル系可塑剤がより好ましく、ポリプロピレングリコールが特に好ましい。
　可塑剤としては１種類のみを使用してもよいし、２種類以上を併用してもよい。 Polymeric plasticizers can also be used as plasticizers. Specific examples of 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.
Among them, polymer plasticizers are preferred, polyether plasticizers are more preferred, and polypropylene glycol is particularly preferred.
As the plasticizer, only one type may be used, or two or more types may be used in combination.
　可塑剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、５～１５０重量部であることが好ましく、１０～１２０重量部がより好ましく、２０～１００重量部が特に好ましい。 The blending amount of the plasticizer is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A). Parts by weight are particularly preferred.
　＜充填剤＞
　硬化性組成物には、充填剤を配合することができる。充填剤の配合によって硬化物の強度を向上させることができる。 <Filler>
A filler can be blended into the curable composition. The strength of the cured product can be improved by adding a filler.
　充填剤としては、重質炭酸カルシウム、膠質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、クレー、タルク、酸化チタン、ヒュームドシリカ、沈降性シリカ、結晶性シリカ、溶融シリカ、無水ケイ酸、含水ケイ酸、アルミナ、カーボンブラック、酸化第二鉄、アルミニウム微粉末、酸化亜鉛、活性亜鉛華、ＰＶＣ粉末、ＰＭＭＡ粉末、ガラス繊維およびフィラメント等が挙げられる。組成物の軽量化（低比重化）の目的で、有機バルーン、無機バルーンを添加してもよい。充填剤としては１種類のみを使用してもよいし、２種類以上を併用してもよい。 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.
　充填剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、１～３００重量部が好ましく、１０～２５０重量部がより好ましい。 The amount of the filler compounded is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
　＜接着性付与剤＞
　硬化性組成物には、接着性付与剤を配合することができる。
　接着性付与剤としては、シランカップリング剤、又は、シランカップリング剤の反応物を添加することができる。 <Adhesion imparting agent>
The curable composition may contain an adhesive agent.
A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
　シランカップリング剤の具体例としては、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルメチルジメトキシシラン、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン、Ｎ－β－アミノエチル－γ－アミノプロピルメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、（２－アミノエチル）アミノメチルトリメトキシシランなどのアミノ基含有シラン類；γ－イソシアネートプロピルトリメトキシシラン、γ－イソシアネートプロピルトリエトキシシラン、γ－イソシアネートプロピルメチルジメトキシシラン、α－イソシアネートメチルトリメトキシシラン、α－イソシアネートメチルジメトキシメチルシラン等のイソシアネート基含有シラン類；γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシラン、γ－メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有シラン類；γ－グリシドキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有シラン類、が挙げられる。また、アミノ基含有シランの縮合物、アミノ基含有シランと他のアルコキシシランとの縮合物、等の各種シランカップリング剤の縮合物；アミノ基含有シランとエポキシ基含有シランの反応物、アミノ基含有シランと（メタ）アクリル基含有シランの反応物、等の各種シランカップリング剤の反応物も使用できる。接着性付与剤は１種類のみで使用しても良いし、２種類以上混合使用しても良い。 Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; . 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.
　接着性付与剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～２０重量部が好ましく、０．５～１０重量部がより好ましい。 The amount of the adhesion-imparting agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
　＜脱水剤＞
　硬化性組成物には、脱水剤を添加することができる。ここで、脱水剤とは、水と反応し得る化合物であることが好ましく、水と反応し得るケイ素化合物（但し接着性付与剤に該当する化合物は除く）がより好ましく、トリアルコキシシラン化合物が特に好ましい。 <Dehydrating agent>
A dehydrating agent can be added to the curable composition. Here, 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.
　前記脱水剤の具体例としては特に限定されないが、メチルトリメトキシシラン、フェニルトリメトキシシラン、ｎ－プロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン等のビニル基含有シラン類等が挙げられる。脱水剤は１種類のみで使用してもよいし、２種類以上使用してもよい。 Specific examples of the dehydrating agent are not particularly limited, but 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.
　脱水剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～２０重量部が好ましく、０．５～１０重量部がより好ましく、１～５重量部がさらに好ましい。 The amount of the dehydrating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1 to 10 parts by weight with respect to 100 parts by weight of the (meth)acrylate copolymer (A). 5 parts by weight is more preferred.
　＜レオロジーコントロール剤＞
　硬化性組成物には、必要に応じてタレを防止し、作業性を良くするためにレオロジーコントロール剤を添加しても良い。 <Rheology control agent>
If necessary, a rheology control agent may be added to the curable composition to prevent sagging and improve workability.
　レオロジーコントロール剤としては特に限定されないが、例えば、脂肪酸アミドワックス類、水添ヒマシ油誘導体類；ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸バリウム等の金属石鹸類；乾式シリカ、湿式シリカ等が挙げられる。これらレオロジーコントロール剤は単独で用いてもよく、２種以上併用してもよい。 Although the 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.
　レオロジーコントロール剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～２０重量部が好ましい。 The content of the rheology control agent is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
　＜酸化防止剤＞
　硬化性組成物には、酸化防止剤（老化防止剤）を使用することができる。酸化防止剤を使用すると硬化物の耐候性を高めることができる。
　酸化防止剤としてはヒンダードフェノール系、モノフェノール系、ビスフェノール系、ポリフェノール系が例示できる。酸化防止剤の具体例は特開平４－２８３２５９号公報や特開平９－１９４７３１号公報にも記載されている。
　酸化防止剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～１０重量部が好ましく、０．２～５重量部がより好ましい。 <Antioxidant>
An antioxidant (antiaging agent) can be used in the curable composition. The use of an antioxidant can enhance the weather resistance of the cured product.
Examples of 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 content of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
　＜光安定剤＞
　硬化性組成物には、光安定剤を使用することができる。光安定剤を使用すると硬化物の光酸化劣化を防止できる。
　光安定剤としてベンゾトリアゾール系、ヒンダードアミン系、ベンゾエート系化合物等が例示できるが、特にヒンダードアミン系が好ましい。
　光安定剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～１０重量部が好ましく、０．２～５重量部がより好ましい。 <Light stabilizer>
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 blending amount of the light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
　＜紫外線吸収剤＞
　硬化性組成物には、紫外線吸収剤を使用することができる。紫外線吸収剤を使用すると硬化物の表面耐候性を高めることができる。
　紫外線吸収剤としてはベンゾフェノン系、ベンゾトリアゾール系、サリチレート系、置換アクリロニトリル系及び金属キレート系化合物等が例示できるが、特にベンゾトリアゾール系が好ましく、市販名チヌビンＰ、チヌビン２１３、チヌビン２３４、チヌビン３２６、チヌビン３２７、チヌビン３２８、チヌビン３２９、チヌビン５７１（以上、ＢＡＳＦ製）が挙げられる。
　紫外線吸収剤の配合量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～１０重量部が好ましく、０．２～５重量部がより好ましい。 <Ultraviolet absorber>
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.
Examples of 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 under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
The blending amount of the ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the (meth)acrylate copolymer (A).
　＜物性調整剤＞
　硬化性組成物には、必要に応じて生成する硬化物の引張特性を調整する物性調整剤を添加しても良い。物性調整剤としては特に限定されないが、例えば、フェノキシトリメチルシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ｎ－プロピルトリメトキシシラン等のアルキルアルコキシシラン類；ジフェニルジメトキシシラン、フェニルトリメトキシシランなどのアリールアルコキシシラン類；ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシラン、γ－グリシドキシプロピルメチルジイソプロペノキシシラン等のアルキルイソプロペノキシシラン；トリス（トリメチルシリル）ボレート、トリス（トリエチルシリル）ボレートなどのトリアルキルシリルボレート類；シリコーンワニス類；ポリシロキサン類等が挙げられる。前記物性調整剤を用いることにより、本実施形態に係る硬化性組成物を硬化させた時の硬度を上げたり、逆に硬度を下げ、破断伸びを出したりし得る。上記物性調整剤は単独で用いてもよく、２種以上併用してもよい。 <Physical property modifier>
A physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition, if necessary. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes; 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.
　特に、加水分解により、分子内に１価のシラノール基を有する化合物を生成する化合物は、硬化物の表面のべたつきを悪化させずに硬化物のモジュラスを低下させる作用を有する。特にトリメチルシラノールを生成する化合物が好ましい。加水分解により分子内に１価のシラノール基を有する化合物を生成する化合物としては、ヘキサノール、オクタノール、フェノール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトールなどのアルコールの誘導体であって加水分解によりシランモノオールを生成するシリコン化合物を挙げることができる。具体的には、フェノキシトリメチルシラン、トリス（（トリメチルシロキシ）メチル）プロパン等が挙げられる。 In particular, 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.
　物性調整剤の使用量は、（メタ）アクリル酸エステル系共重合体（Ａ）１００重量部に対して、０．１～１０重量部が好ましく、０．５～５重量部がより好ましい。 The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic acid ester copolymer (A).
　＜＜硬化性組成物＞＞
　本発明の一実施形態に係る硬化性組成物は、すべての配合成分を予め配合して密封保存し、施工後空気中の湿気により硬化する１成分型として調製することができる。この場合、水分を含有する配合成分は予め脱水乾燥してから使用するか、又は、配合混練中に減圧などにより脱水することが好ましい。 <<Curable composition>>
The curable composition according to one embodiment of the present invention can be prepared as a one-component type in which all ingredients are pre-blended and stored in a sealed container, and cured by moisture in the air after application. In this case, it is preferable that the ingredients containing water are dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and kneading.
　また、本発明の一実施形態に係る硬化性組成物は、（メタ）アクリル酸エステル系共重合体（Ａ）と粘着付与樹脂（Ｂ）を含む主剤と、シラノール縮合触媒、充填剤、可塑剤、水等の成分を含む硬化剤から構成され、該主剤と硬化剤を使用前に混合する２成分型として調製することもできる。 Further, the curable composition according to one embodiment of the present invention includes a main agent containing a (meth)acrylic acid ester copolymer (A) and a tackifier resin (B), a silanol condensation catalyst, a filler, and a plasticizer. , water, etc., and can be prepared as a two-component type in which the main agent and the curing agent are mixed before use.
　本発明の一実施形態に係る硬化性組成物の調製法には特に限定はない。例えば、上記各成分を配合し、ミキサー、ロール、ニーダーなどを用いて常温または加熱下で混練したり、適切な溶剤を少量使用して上記各成分を溶解させ、混合したりするなどの通常の方法が採用され得る。 The method for preparing the curable composition according to one embodiment of the present invention is not particularly limited. For example, the above components are blended and kneaded at room temperature or under heating using a mixer, roll, kneader, etc., or a small amount of an appropriate solvent is used to dissolve and mix the above components. methods can be employed.
　本発明の一実施形態に係る硬化性組成物は、プラスチック、金属、複合材などの様々な被着体に対して良好な接着性を示すことができる。また、ポリプロピレンなどの非極性材料やポリフェニレンサルファイドなどの剛直な分子鎖を有するエンジニアリングプラスチックに対する接着剤として使用する場合には、これら被着体に対する接着性を高め、安定した接着強度を得るために、被着体を公知の方法で事前に表面処理することができる。例えば、サンディング処理、フレーム処理、コロナ放電、アーク放電、プラズマ処理などの表面処理技術を使うことができる。被着体へのダメージが少なく、安定した接着性が得られることから、プラズマ処理が好ましい。これらの表面処理は、成形時に使用され被着体表面に残存している離型剤を除去するためにも有効である。 The curable composition according to one embodiment of the present invention can exhibit good adhesion to various adherends such as plastics, metals and composite materials. In addition, when used as an adhesive for non-polar materials such as polypropylene and engineering plastics with rigid molecular chains such as polyphenylene sulfide, in order to increase adhesion to these adherends and obtain stable adhesive strength, 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 less 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.
　本発明の一実施形態に係る硬化性組成物を硬化して得られる硬化物は、種々の被着体に対して良好な接着性を有することから、該硬化性組成物は、接着剤、シーリング材、又は、粘着剤として用いることができる。特に、本発明の一実施形態に係る硬化性組成物は、比較的低温では粘度が高いにも関わらず、比較的高温になると粘度が格段に低下し得るとの特性を利用して、ホットメルト型硬化性組成物、又は粘着剤組成物として好適に使用することかできる。 Since the cured product obtained by curing the curable composition according to one embodiment of the present invention has good adhesion to various adherends, the curable composition can be used as an adhesive, a sealing It can be used as a material or an adhesive. In particular, the curable composition according to one embodiment of the present invention has a high viscosity at a relatively low temperature, but the viscosity can be significantly reduced at a relatively high temperature. It can be suitably used as a mold curable composition or an adhesive composition.
　本発明の一実施形態に係る硬化性組成物は、被着体に塗布する際には作業性を確保するため、高温に加熱して粘度を低下させることが好ましく、その際の温度としては、７０～１８０℃程度が好ましく、９０～１６０℃がより好ましく、１００～１５０℃がさらに好ましい。加熱する方法としては特に制限されず、従来公知の方法を用いることができる。 The curable composition according to one embodiment of the present invention is preferably heated to a high temperature to reduce the viscosity in order to ensure workability when applied to an adherend. About 70 to 180°C is preferable, 90 to 160°C is more preferable, and 100 to 150°C is even more preferable. The heating method is not particularly limited, and conventionally known methods can be used.
　本発明の一実施形態に係る硬化性組成物は、被着体を接合した後、長時間の硬化（養生）工程を行うことで、目的の物性を発現することができる。当該硬化（養生）工程の条件としては特に限定されないが、例えば、温度として５～９０℃、時間として２４時間～１週間などが挙げられる。 The curable composition according to one embodiment of the present invention can express the desired physical properties by performing a long-term curing (curing) process after bonding the adherends. The conditions for the curing (curing) step are not particularly limited, but include, for example, a temperature of 5 to 90° C. and a time of 24 hours to 1 week.
　本発明の一実施形態に係る硬化性組成物をホットメルト型硬化性組成物として使用する場合には、反応性ホットメルト接着剤として使用することができる。本硬化性組成物は、バス、トレーラー、電車などのパネルを接合するための接着剤として、スマートフォンやタブレット端末、ノートパソコンなどにおけるディスプレイと筐体との接着剤として、また、アルミニウム－スチール、スチール－複合材、アルミニウム－複合材などの異種材料を接合する用途にも適している。異種材料の接合では腐食を防止するために接合部をシーラーで覆うことが好ましい。シーラーとしては、本願で示したような反応性ケイ素基を有する重合体を使用することが可能である。 When the curable composition according to one embodiment of the present invention is used as a hot-melt curable composition, it can be used as a reactive hot-melt adhesive. This curable composition can be used as an adhesive for joining panels of buses, trailers, trains, etc., as an adhesive for displays and housings in smartphones, tablet terminals, laptop computers, etc. -Also suitable for joining dissimilar materials such as composites and aluminum-composites. When dissimilar materials are joined, it is preferable to cover the joint with a sealer to prevent corrosion. As a sealer, it is possible to use a polymer having reactive silicon groups as shown in this application.
　本発明の一実施形態に係る硬化性組成物は、より具体的には、車両パネルなどの自動車部品、トラック、バスなど大型車両部品、列車車両用部品、航空機部品、船舶用部品、電機部品、各種機械部品などにおいて使用される接着剤として使用されることが好ましい。 More specifically, the curable composition according to one embodiment of the present invention can be It is preferably used as an adhesive used in various machine parts.
　本発明の一実施形態に係る硬化性組成物を粘着剤組成物として使用する場合、事務一般用、紙オムツ用、ＰＰフィルム接着用、再剥離用、一般包装用、電気用、固定用の各種粘着製品用途に使用可能である。本発明の一実施形態に係る粘着剤組成物を含む粘着製品は、包装用粘着テープ、事務用粘着テープ、塗装マスキング用テープ、電気絶縁用粘着テープ、結束用粘着テープ、保護用粘着テープ、識別・装飾用粘着テープ及びシート、スポーツテープ、両面粘着テープ、電磁波障害対策フィルム及びテープ、再剥離フィルム及びテープ、化粧板フィルム、半導体チップ搬送用テープ、マーキングフィルム、深絞り加工用保護フィルム、ガラス飛散防止フィルム、発泡粘着テープ、防水・止水テープ、防食用粘着テープ、表面保護用粘着テープ、ダイシング用粘着テープ、バックグラインド用粘着テープ、印刷用粘着シート、粘着ラベル等が挙げられる。 When the curable composition according to one embodiment of the present invention is used as an adhesive composition, it can be used for general office work, paper diapers, PP film adhesion, removability, general packaging, electrical use, and fixing. Can be used for adhesive products. Adhesive products containing the adhesive composition according to one embodiment of the present invention include packaging adhesive tapes, office adhesive tapes, paint masking tapes, electrical insulating adhesive tapes, binding adhesive tapes, protective adhesive tapes, identification・Decorative adhesive tapes and sheets, sports tapes, double-sided adhesive tapes, electromagnetic wave interference countermeasure films and tapes, removable films and tapes, veneer films, semiconductor chip transport tapes, marking films, protective films for deep drawing, glass scattering Prevention films, foamed adhesive tapes, waterproof/water-stopping tapes, anti-corrosion adhesive tapes, surface-protecting adhesive tapes, dicing adhesive tapes, back-grinding adhesive tapes, printing adhesive sheets, adhesive labels, and the like.
　以下の各項目では、本開示における好ましい態様を列挙するが、本発明は以下の項目に限定されるものではない。
［項目１］
　下記一般式（１）で表される反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）、及び、
　粘着付与樹脂（Ｂ）を含有し、
　前記（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分が、
（メタ）アクリル酸エステル（ａ１）、
（メタ）アクリロイル基を分子内に１つより多く有する重合体（ａ２）、及び、
メルカプト基を有する連鎖移動剤（ａ３）、を含有し、
　前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）をさらに含有し、及び／又は、前記メルカプト基を有する連鎖移動剤（ａ３）が、反応性ケイ素基をさらに有する、硬化性組成物。
－ＳｉＲ１ ３－ａＸａ　　　　（１）
（式中、Ｒ１は、置換又は非置換の炭素数１～２０の炭化水素基を表す。Ｘは水酸基または加水分解性基を表す。ａは２または３である。）
［項目２］
　前記粘着付与樹脂（Ｂ）が、ロジン系樹脂、テルペン系樹脂、石油系樹脂、アルキルフェノール樹脂、及び、芳香族系炭化水素樹脂からなる群より選択される少なくとも１種以上の樹脂を含有する、項目１に記載の硬化性組成物。
［項目３］
　重合体（ａ２）が、（メタ）アクリロイル基を分子内に１つより多く有するポリオキシアルキレン系重合体（ａ２″）である、項目１又は２に記載の硬化性組成物。
［項目４］
　重合体（ａ２）が、（メタ）アクリロイル基を分子内に１つより多く有する（メタ）アクリル酸エステル系重合体（ａ２′）である、項目１又は２に記載の硬化性組成物。
［項目５］
　重合体（ａ２）／メルカプト基を有する連鎖移動剤（ａ３）のモル比が０．０５以上である、項目１～４のいずれか１項に記載の硬化性組成物。
［項目６］
　ホットメルト型硬化性組成物である、項目１～５のいずれか１項に記載の硬化性組成物。
［項目７］
　粘着剤組成物である、項目１～６のいずれか１項に記載の硬化性組成物。
［項目８］
　前記粘着付与樹脂（Ｂ）が、ロジン系樹脂、及び、テルペン系樹脂からなる群より選択される少なくとも１種以上の樹脂を含有する、項目７に記載の硬化性組成物。
［項目９］
　項目１～８のいずれか１項に記載の硬化性組成物を硬化させて得られる硬化物。 The following items list preferred embodiments in the present disclosure, but the present invention is not limited to the following items.
[Item 1]
(Meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and
Containing a tackifying resin (B),
The monomer component constituting the (meth)acrylic acid ester copolymer (A) is
(meth) acrylic acid ester (a1),
A polymer (a2) having more than one (meth)acryloyl group in the molecule, and
containing a chain transfer agent (a3) having a mercapto group,
The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon A curable composition further comprising a group.
—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 is 2 or 3.)
[Item 2]
The tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins, terpene-based resins, petroleum-based resins, alkylphenol resins, and aromatic hydrocarbon resins. 1. The curable composition according to 1.
[Item 3]
3. The curable composition according to item 1 or 2, wherein the polymer (a2) is a polyoxyalkylene polymer (a2″) having more than one (meth)acryloyl group in the molecule.
[Item 4]
3. The curable composition according to item 1 or 2, wherein the polymer (a2) is a (meth)acrylate polymer (a2') having more than one (meth)acryloyl group in the molecule.
[Item 5]
5. The curable composition according to any one of items 1 to 4, wherein the molar ratio of polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.05 or more.
[Item 6]
The curable composition according to any one of items 1 to 5, which is a hot-melt curable composition.
[Item 7]
The curable composition according to any one of items 1 to 6, which is an adhesive composition.
[Item 8]
Item 8. The curable composition according to item 7, wherein the tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins and terpene-based resins.
[Item 9]
A cured product obtained by curing the curable composition according to any one of items 1 to 8.
　以下に、実施例を掲げて本発明を具体的に説明するが、本実施例は本発明を限定するものではない。 Although the present invention will be specifically described below with reference to examples, the present examples are not intended to limit the present invention.
　実施例中の数平均分子量及び重量平均分子量は、以下の条件で測定したＧＰＣ分子量である。
　　送液システム：東ソー製ＨＬＣ－８１２０ＧＰＣ
　　カラム：東ソー製ＴＳＫ－ＧＥＬ　Ｈタイプ
　　溶媒：ＴＨＦ
　　分子量：ポリスチレン換算
　　測定温度：４０℃ 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
　実施例中の末端基換算分子量は、水酸基価をＪＩＳ　Ｋ　１５５７の測定方法により、ヨウ素価をＪＩＳ　Ｋ　００７０の測定方法により求め、有機重合体の構造（使用した重合開始剤によって定まる分岐度）を考慮して求めた分子量である。 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.
　実施例に示す重合体の末端１個あたりへの炭素－炭素不飽和結合の平均導入数は、以下の計算式により算出した。
（平均導入数）＝[ヨウ素価から求めた重合体の不飽和基濃度（ｍｏｌ／ｇ）－ヨウ素価から求めた前駆重合体の不飽和基濃度（ｍｏｌ／ｇ）]／［水酸基価から求めた前駆重合体の水酸基濃度（ｍｏｌ／ｇ）］ 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)]
　（硫黄原子濃度）
　硫黄原子濃度は、（メタ）アクリル酸エステル系共重合体（Ａ）の製造に使用した単量体成分の合計量と、メルカプト基を有する連鎖移動剤（ａ３）の量から算出した理論値である。 (sulfur atom concentration)
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 (A) and the amount of the chain transfer agent (a3) having a mercapto group. be.
　（合成例１）
　数平均分子量が約４，０２０（末端基換算分子量２，９８０）のポリオキシプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキサイドの重合を行い、両末端に水酸基を有し、数平均分子量２１，１００（末端基換算分子量１３，６００）、分子量分布Ｍｗ／Ｍｎ＝１．２１のポリオキシプロピレンを得た。得られたポリオキシプロピレンにＵ－３６０（ジブチル錫ビス（イソオクチルメルカプトプロピオネート、日東化成（株））を６０ｐｐｍ添加し、ポリオキシプロピレンの水酸基に対してカレンズＡＯＩ（２－イソシアナートエチルアクリレート、昭和電工（株））を０．９３当量滴下し、５．５％の酸素を含んだ窒素雰囲気中で、８０℃で１時間反応を行い、両末端にアクリロイル基を有し（即ち、重合体１分子中に約２個のアクリロイル基を有し）、数平均分子量が２１，１００、重量平均分子量が２４，９３０であるポリオキシアルキレン系重合体である多官能性マクロモノマー（ａ２－１）を得た。 (Synthesis example 1)
Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal groups: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to have hydroxyl groups at both ends. , a number average molecular weight of 21,100 (termed molecular weight of terminal groups: 13,600) and a molecular weight distribution Mw/Mn of 1.21. 60 ppm of U-360 (dibutyltin bis (isooctyl mercaptopropionate, Nitto Kasei Co., Ltd.)) was added to the obtained polyoxypropylene, and Karenz AOI (2-isocyanato ethyl acrylate , Showa Denko Co., Ltd.) was dropped in an amount of 0.93 equivalents, and the mixture was reacted at 80°C for 1 hour in a nitrogen atmosphere containing 5.5% oxygen. Polyfunctional macromonomer (a2-1) which is a polyoxyalkylene polymer having about two acryloyl groups in one combined molecule), a number average molecular weight of 21,100, and a weight average molecular weight of 24,930 ).
　（合成例２）
　攪拌機を備えた四口フラスコにイソブタノール４５．０重量部を入れ、窒素雰囲気下、１０５℃まで昇温した。そこに、メチルメタクリレート４１．５重量部、ブチルアクリレート４．０重量部、ステアリルメタクリレート４．０重量部、３－メタクリロキシプロピルトリメトキシシラン４．１重量部、合成例１で作製した多官能性マクロモノマー（ａ２－１）４３．８重量部、３－メルカプトプロピルトリメトキシシラン２．６重量部、及び２，２’－アゾビス（２－メチルブチロニトリル）０．９重量部をイソブタノール２８．３重量部に溶解した混合溶液を５時間かけて滴下した。さらに２，２’－アゾビス（２－メチルブチロニトリル）０．３重量部をイソブタノール９．４重量部に溶解した混合溶液を加え１０５℃で２時間重合を行い、数平均分子量が４，３９０、重量平均分子量が２９，９５０（ＧＰＣ分子量）である反応性ケイ素基含有（メタ）アクリル酸エステル系共重合体（Ａ－１）のイソブタノール溶液（固形分５５％）を得た。当該溶液の固形分の多官能性マクロモノマー当量は０．０２１ｍｍｏｌ／ｇ、反応性ケイ素基当量は０．３０ｍｍｏｌ／ｇであり、硫黄原子濃度は４，２３８ｐｐｍである。 (Synthesis example 2)
A four-necked flask equipped with a stirrer was charged with 45.0 parts by weight of isobutanol, and the temperature was raised to 105° C. under a nitrogen atmosphere. There, 41.5 parts by weight of methyl methacrylate, 4.0 parts by weight of butyl acrylate, 4.0 parts by weight of stearyl methacrylate, 4.1 parts by weight of 3-methacryloxypropyltrimethoxysilane, the polyfunctional 43.8 parts by weight of the macromonomer (a2-1), 2.6 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.9 parts by weight of 2,2'-azobis(2-methylbutyronitrile) were mixed with 28 parts by weight of isobutanol. A mixed solution dissolved in .3 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 9.4 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 390 and a weight average molecular weight of 29,950 (GPC molecular weight), an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) was obtained. The solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.30 mmol/g, and a sulfur atom concentration of 4,238 ppm.
　（合成例３）
　脱酸素状態にした反応器に、臭化第一銅０．４２重量部、ブチルアクリレート２０．０重量部を添加し、加熱攪拌した。重合溶媒としてアセトニトリル８．８重量部、開始剤としてジエチル２，５－ジブロモアジペート３．１重量部を添加、混合し、混合液の温度を約８０℃に調節した段階でペンタメチルジエチレントリアミン（以下、トリアミンと略す）を添加し、重合反応を開始した。次いで、ブチルアクリレート８０．０重量部を逐次添加し、重合反応を進めた。重合途中、適宜トリアミンを追加し、重合速度を調整した。重合時に使用したトリアミンの総量は０．１５重量部であった。モノマー転化率（重合反応率）が約９５％以上の時点で揮発分を減圧脱揮して除去し、重合体濃縮物を得た。
　上記濃縮物をトルエンで希釈し、ろ過助剤、吸着剤（キョーワード７００ＳＥＮ：協和化学製）、ハイドロタルサイト（キョーワード５００ＳＨ：協和化学製）を添加し、８０～１００℃程度に加熱攪拌した後、固形成分を濾過除去した。ろ液を減圧濃縮し、重合体粗精製物を得た。
　重合体粗精製物、アクリル酸カリウム３．８重量部、４－ヒドロキシ－ＴＥＭＰＯ１００ｐｐｍ、溶剤としてジメチルアセトアミド１００重量部を添加し、７０℃で３時間反応させた後、溶媒を減圧留去し重合体濃縮物を得た。濃縮物をトルエンで希釈し、固形成分を濾過除去した。ろ液を減圧濃縮し、両末端にアクリロイル基を有し（即ち、重合体１分子中に２つのアクリロイル基を有し）、数平均分子量が１１，４１０（ＧＰＣ分子量）、分子量分布（Ｍｗ／Ｍｎ）が１．２７である（メタ）アクリル酸エステル系重合体である多官能性マクロモノマー（ａ２－２）を得た。 (Synthesis Example 3)
0.42 parts by weight of cuprous bromide and 20.0 parts by weight of butyl acrylate were added to the deoxygenated reactor and heated with stirring. 8.8 parts by weight of acetonitrile as a polymerization solvent and 3.1 parts by weight of diethyl 2,5-dibromoadipate as an initiator were added and mixed, and at the stage where the temperature of the mixture was adjusted to about 80° C., pentamethyldiethylenetriamine (hereinafter referred to as abbreviated as triamine) was added to initiate the polymerization reaction. Then, 80.0 parts by weight of butyl acrylate was successively added to proceed with the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during polymerization was 0.15 parts by weight. When the monomer conversion rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed under reduced pressure to obtain a polymer concentrate.
The above concentrate was diluted with toluene, a filter aid, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Kagaku), and hydrotalcite (Kyoward 500SH: manufactured by Kyowa Kagaku) were added, and the mixture was heated and stirred at about 80 to 100°C. After that, solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude polymer product.
Add 3.8 parts by weight of crude polymer, 3.8 parts by weight of potassium acrylate, 100 ppm of 4-hydroxy-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent, and react at 70° C. for 3 hours. A concentrate was obtained. The concentrate was diluted with toluene and the solid components were filtered off. The filtrate was concentrated under reduced pressure, having acryloyl groups at both ends (that is, having two acryloyl groups in one polymer molecule), a number average molecular weight of 11,410 (GPC molecular weight), and a molecular weight distribution (Mw/ A polyfunctional macromonomer (a2-2), which is a (meth)acrylic acid ester polymer having Mn) of 1.27, was obtained.
　（合成例４）
　攪拌機を備えた四口フラスコにイソブタノール４８．７重量部を入れ、窒素雰囲気下、１０５℃まで昇温した。そこに、メチルメタクリレート４２．０重量部、ブチルアクリレート０．５重量部、２－エチルヘキシルアクリレート８．５重量部、ステアリルメタクリレート０．５重量部、３－メタクリロキシプロピルトリメトキシシラン０．５重量部、合成例１で作製した多官能性マクロモノマー（ａ２－１）４５．０重量部、３－メルカプトプロピルトリメトキシシラン３．０重量部、及び２，２’－アゾビス（２－メチルブチロニトリル）０．５重量部をイソブタノール１２．０重量部に溶解した混合溶液を５時間かけて滴下した。さらに２，２’－アゾビス（２－メチルブチロニトリル）０．３５重量部をイソブタノール６．７重量部に溶解した混合溶液を加え１０５℃で２時間重合を行い、数平均分子量が４，０４０、重量平均分子量が３０，１８０（ＧＰＣ分子量）である反応性ケイ素基含有（メタ）アクリル酸エステル系共重合体（Ａ－２）のイソブタノール溶液（固形分５５％）を得た。当該溶液の固形分の多官能性マクロモノマー当量は０．０２１ｍｍｏｌ／ｇ、反応性ケイ素基当量は０．１７ｍｍｏｌ／ｇであり、硫黄原子濃度は４，８９０ｐｐｍである。 (Synthesis Example 4)
A four-neck flask equipped with a stirrer was charged with 48.7 parts by weight of isobutanol, and the temperature was raised to 105° C. under a nitrogen atmosphere. 42.0 parts by weight of methyl methacrylate, 0.5 parts by weight of butyl acrylate, 8.5 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of stearyl methacrylate, and 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane. , 45.0 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 1, 3.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2,2′-azobis(2-methylbutyronitrile ) dissolved in 12.0 parts by weight of isobutanol was added dropwise over 5 hours. Further, a mixed solution of 0.35 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.7 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 040 and a weight average molecular weight of 30,180 (GPC molecular weight), an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylate copolymer (A-2) was obtained. The solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.17 mmol/g, and a sulfur atom concentration of 4,890 ppm.
　（合成例５）
　攪拌機を備えた四口フラスコにイソブタノール４８．７重量部を入れ、窒素雰囲気下、１０５℃まで昇温した。そこに、メチルメタクリレート４２．０重量部、ブチルアクリレート０．５重量部、２－エチルヘキシルアクリレート８．５重量部、ステアリルメタクリレート０．５重量部、３－メタクリロキシプロピルジメトキシメチルシラン０．５重量部、合成例３で作製した多官能性マクロモノマー（ａ２－２）４５．０重量部、３－メルカプトプロピルジメトキシメチルシラン３．０重量部、及び２，２’－アゾビス（２－メチルブチロニトリル）０．５重量部をイソブタノール１２．０重量部に溶解した混合溶液を５時間かけて滴下した。さらに２，２’－アゾビス（２－メチルブチロニトリル）０．３５重量部をイソブタノール６．７重量部に溶解した混合溶液を加え１０５℃で２時間重合を行い、数平均分子量が３，９００、重量平均分子量が２９，５００（ＧＰＣ分子量）である反応性ケイ素基含有（メタ）アクリル酸エステル系共重合体（Ａ－３）のイソブタノール溶液（固形分５５％）を得た。当該溶液の固形分の多官能性マクロモノマー当量は０．０２１ｍｍｏｌ／ｇ、反応性ケイ素基当量は０．１９ｍｍｏｌ／ｇであり、硫黄原子濃度は５，３２０ｐｐｍである。 (Synthesis Example 5)
A four-neck flask equipped with a stirrer was charged with 48.7 parts by weight of isobutanol, and the temperature was raised to 105° C. under a nitrogen atmosphere. 42.0 parts by weight of methyl methacrylate, 0.5 parts by weight of butyl acrylate, 8.5 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of stearyl methacrylate, and 0.5 parts by weight of 3-methacryloxypropyldimethoxymethylsilane. , 45.0 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 3, 3.0 parts by weight of 3-mercaptopropyldimethoxymethylsilane, and 2,2′-azobis(2-methylbutyronitrile ) dissolved in 12.0 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.35 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.7 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 900 and a weight average molecular weight of 29,500 (GPC molecular weight), an isobutanol solution (solid content: 55%) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-3) was obtained. The solid content of the solution has a polyfunctional macromonomer equivalent weight of 0.021 mmol/g, a reactive silicon group equivalent weight of 0.19 mmol/g, and a sulfur atom concentration of 5,320 ppm.
　（実施例１）
　合成例２で得られた（メタ）アクリル酸エステル系共重合体（Ａ－１）のイソブタノール溶液に、固形分１００重量部に対して、粘着付与樹脂（Ｂ）としてＹＳポリスターＴ８０（テルペンフェノール樹脂、ヤスハラケミカル（株）製）３０重量となるように混合した後、イソブタノールを加熱脱揮して混合物を得た後、下記方法で該混合物の粘度を測定した。得られた結果を表１に示す。 (Example 1)
YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed to 30 weight, and the isobutanol was devolatilized by heating to obtain a mixture, and the viscosity of the mixture was measured by the following method. Table 1 shows the results obtained.
　（粘度）
　治具として直径２０ｍｍの平行円板プレートを用い、ギャップを０．３ｍｍ、せん断速度を１（１／ｓｅｃ）とし、６０℃から１５０℃まで５℃／ｍｉｎで昇温しながら粘度測定を実施した。粘度は、６０℃及び１２０℃での値を読み取った。 (viscosity)
A parallel disk plate with a diameter of 20 mm was used as a jig, the gap was set to 0.3 mm, the shear rate was set to 1 (1/sec), and the viscosity was measured while increasing the temperature from 60° C. to 150° C. at a rate of 5° C./min. . The viscosity was read at 60°C and 120°C.
　（実施例２）
　粘着付与樹脂（Ｂ）としてＤ－６０１１（ロジン系樹脂、荒川化学工業株式会社製）を使用した以外は実施例１と同様に混合物を作製し、該混合物の粘度を実施例１と同様に測定した。得られた結果を表１に示す。 (Example 2)
A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin resin, manufactured by Arakawa Chemical Industries, Ltd.) was used as the tackifier resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. bottom. Table 1 shows the results obtained.
　（実施例３）
　粘着付与樹脂（Ｂ）としてＦＴＲ６１２５（芳香族系炭化水素樹脂、三井化学（株）製）５０重量部を配合した以外は実施例１と同様に混合物を作製し、該混合物の粘度を実施例１と同様に測定した。得られた結果を表１に示す。 (Example 3)
A mixture was prepared in the same manner as in Example 1 except that 50 parts by weight of FTR6125 (aromatic hydrocarbon resin, manufactured by Mitsui Chemicals, Inc.) was blended as the tackifying resin (B), and the viscosity of the mixture was measured in Example 1. was measured in the same manner as Table 1 shows the results obtained.
　（実施例４）
　粘着付与樹脂（Ｂ）として日赤ネオポリマー（芳香族系炭化水素樹脂、ＥＮＥＯＳ製）を使用した以外は実施例１と同様に混合物を作製し、該混合物の粘度を実施例１と同様に測定した。得られた結果を表１に示す。 (Example 4)
A mixture was prepared in the same manner as in Example 1 except that Nisseki Neopolymer (aromatic hydrocarbon resin, manufactured by ENEOS) was used as the tackifying resin (B), and the viscosity of the mixture was measured in the same manner as in Example 1. . Table 1 shows the results obtained.
　（比較例１）
　粘着付与樹脂（Ｂ）を使用せず、合成例２で得られた（メタ）アクリル酸エステル系共重合体（Ａ－１）のイソブタノール溶液からイソブタノールを加熱脱揮し、得られた共重合体（Ａ－１）の粘度を実施例１と同様に測定した。得られた結果を表１に示す。 (Comparative example 1)
Without using the tackifying resin (B), isobutanol was heated and devolatilized from the isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 2, and the copolymer obtained The viscosity of polymer (A-1) was measured in the same manner as in Example 1. Table 1 shows the results obtained.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１から、（メタ）アクリル酸エステル系共重合体（Ａ）と粘着付与樹脂（Ｂ）を含有する実施例１～４の硬化性組成物は、比較例１の（メタ）アクリル酸エステル系共重合体（Ａ）と比べて低温（６０℃）での粘度は高いにも関わらず、高温（１２０℃）での粘度が低いことが分かる。このことから、実施例１～４の硬化性組成物は、ホットメルト型接着剤に適していると言える。 From Table 1, the curable compositions of Examples 1 to 4 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 1. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). From this, it can be said that the curable compositions of Examples 1 to 4 are suitable for hot melt adhesives.
　（実施例５）
　合成例４で得られた（メタ）アクリル酸エステル系共重合体（Ａ－２）のイソブタノール溶液に、固形分１００重量部に対して、粘着付与樹脂（Ｂ）としてＹＳポリスターＴ８０（テルペンフェノール樹脂、ヤスハラケミカル（株）製）６０重量となるように混合した後、イソブタノールを加熱脱揮して混合物を得、硬化触媒としてネオスタンＵ－２０（ジブチル錫ジブチルマレエート、日東化成（株）製）を混合した後、上記方法で該混合物の粘度を測定した。得られた結果を表２に示す。 (Example 5)
YS Polystar T80 (terpene phenol Resin, manufactured by Yasuhara Chemical Co., Ltd.) was mixed so as to have a weight of 60, and the isobutanol was heated and devolatilized to obtain a mixture. ) were mixed, and the viscosity of the mixture was measured by the method described above. Table 2 shows the results obtained.
　（実施例６）
　粘着付与樹脂（Ｂ）としてＤ－６０１１（ロジン系樹脂、荒川化学工業株式会社製、酸価：０）を使用した以外は実施例１と同様に混合物を作製し、該混合物の粘度を実施例５と同様に測定した。得られた結果を表２に示す。 (Example 6)
A mixture was prepared in the same manner as in Example 1 except that D-6011 (rosin-based resin, manufactured by Arakawa Chemical Industries, Ltd., acid value: 0) was used as the tackifier resin (B), and the viscosity of the mixture was measured in Examples. Measured in the same manner as in 5. Table 2 shows the results obtained.
　（実施例７）
　合成例５で得られた（メタ）アクリル酸エステル系共重合体（Ａ－３）のイソブタノール溶液に、固形分１００重量部に対して、粘着付与樹脂（Ｂ）としてＤ－６０１１（ロジン系樹脂、荒川化学工業株式会社製）４０重量となるように混合した後、イソブタノールを加熱脱揮して混合物を得、硬化触媒としてネオスタンＵ－２０（ジブチル錫ジブチルマレエート、日東化成（株）製）、アミン化合物としてＮ，Ｎ－ジエチル－１，３－プロパンジアミンを混合した後、該混合物の粘度を実施例５と同様に測定した。得られた結果を表２に示す。 (Example 7)
D-6011 (rosin-based Resin, manufactured by Arakawa Chemical Industries Co., Ltd.) was mixed to 40 weight, then isobutanol was heated and devolatilized to obtain a mixture. The viscosity of the mixture was measured in the same manner as in Example 5 after mixing N,N-diethyl-1,3-propanediamine as an amine compound. Table 2 shows the results obtained.
　（比較例２）
　粘着付与樹脂（Ｂ）を使用せず、合成例４で得られた（メタ）アクリル酸エステル系共重合体（Ａ－２）のイソブタノール溶液からイソブタノールを加熱脱揮し、得られた共重合体（Ａ－２）の粘度を実施例５と同様に測定した。得られた結果を表２に示す。 (Comparative example 2)
Without using the tackifying resin (B), isobutanol was heated and devolatilized from the isobutanol solution of the (meth)acrylic acid ester copolymer (A-2) obtained in Synthesis Example 4, and the copolymer obtained The viscosity of polymer (A-2) was measured in the same manner as in Example 5. Table 2 shows the results obtained.
　（剥離強度の測定）
　２００ｍｍ×２５ｍｍ、厚さ０．１ｍｍのアルミ箔に、１５０℃に加熱した混合物を厚みが約３００μｍとなるように塗布した。塗布したアルミ箔を８０℃で１５分加熱し、混合物を硬化させた。２３℃５０％ＲＨ条件下で１時間放置した後に、ステンレス板（１００ｍｍ×２５ｍｍ×１．６ｍｍ）に貼り合わせた。アルミ箔面を上にして５ｋｇのローラーを用いて１０往復し、アルミ箔とステンレス板を密着させ、２３℃５０％ＲＨ条件下で２４時間放置した。アルミ箔とステンレス板が１８０°となるように引張り試験を実施し、剥離強度を測定した。破壊状態は、凝集破壊（粘着剤部分で破壊）をＣＦ、界面破壊（粘着剤とステンレス板との界面で剥離）をＡＦとし、目視で確認した。引張り試験は（株）島津製オートグラフ（ＡＧＳ－Ｘ）を用い３００ｍｍ／ｍｉｎの引張り速度で測定を行った。結果を表２に示す。 (Measurement of peel strength)
The mixture heated to 150° C. was applied to an aluminum foil having a size of 200 mm×25 mm and a thickness of 0.1 mm so as to have a thickness of about 300 μm. The coated aluminum foil was heated at 80° C. for 15 minutes to cure the mixture. After being left under conditions of 23° C. and 50% RH for 1 hour, it was attached to a stainless steel plate (100 mm×25 mm×1.6 mm). With the aluminum foil surface facing up, a roller of 5 kg was reciprocated 10 times to bring the aluminum foil and the stainless steel plate into close contact with each other, and allowed to stand at 23° C. and 50% RH for 24 hours. A tensile test was performed so that the aluminum foil and the stainless steel plate were at 180°, and the peel strength was measured. The state of destruction was visually confirmed with CF representing cohesive failure (destruction at the adhesive portion) and AF representing interfacial failure (separation at the interface between the adhesive and the stainless steel plate). The tensile test was performed using an autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 300 mm/min. Table 2 shows the results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２から、（メタ）アクリル酸エステル系共重合体（Ａ）と粘着付与樹脂（Ｂ）を含有する実施例５～７の硬化性組成物は、比較例２の（メタ）アクリル酸エステル系共重合体（Ａ）と比べて低温（６０℃）での粘度は高いにも関わらず、高温（１２０℃）での粘度が低いことが分かる。また、実施例５～７の硬化性組成物は、比較例２と比べてピール試験における剥離強度が高いことが分かる。以上から、実施例５～７の硬化性組成物は、粘着剤に適していると言える。 From Table 2, the curable compositions of Examples 5 to 7 containing the (meth)acrylic acid ester copolymer (A) and the tackifying resin (B) are the (meth)acrylic acid ester-based compositions of Comparative Example 2. It can be seen that the viscosity at high temperatures (120° C.) is low, although the viscosity at low temperatures (60° C.) is higher than that of copolymer (A). In addition, it can be seen that the curable compositions of Examples 5 to 7 have higher peel strength in the peel test than Comparative Example 2. From the above, it can be said that the curable compositions of Examples 5 to 7 are suitable for adhesives.

Claims (9)

  1. 　下記一般式（１）で表される反応性ケイ素基を有する（メタ）アクリル酸エステル系共重合体（Ａ）、及び、
    　粘着付与樹脂（Ｂ）を含有し、
    　前記（メタ）アクリル酸エステル系共重合体（Ａ）を構成する単量体成分が、
    （メタ）アクリル酸エステル（ａ１）、
    （メタ）アクリロイル基を分子内に１つより多く有する重合体（ａ２）、及び、
    メルカプト基を有する連鎖移動剤（ａ３）、を含有し、
    　前記単量体成分が、反応性ケイ素基と重合性不飽和基を有する単量体（ａ４）をさらに含有し、及び／又は、前記メルカプト基を有する連鎖移動剤（ａ３）が、反応性ケイ素基をさらに有する、硬化性組成物。
    －ＳｉＲ１ ３－ａＸａ　　　　（１）
    （式中、Ｒ１は、置換又は非置換の炭素数１～２０の炭化水素基を表す。Ｘは水酸基または加水分解性基を表す。ａは２または３である。）     (Meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following general formula (1), and
    Containing a tackifying resin (B),
    The monomer component constituting the (meth)acrylic acid ester copolymer (A) is
    (meth) acrylic acid ester (a1),
    A polymer (a2) having more than one (meth)acryloyl group in the molecule, and
    containing a chain transfer agent (a3) having a mercapto group,
    The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and/or the chain transfer agent (a3) having a mercapto group is a reactive silicon A curable composition further comprising a group.
    —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 is 2 or 3.)
  2. 　前記粘着付与樹脂（Ｂ）が、ロジン系樹脂、テルペン系樹脂、石油系樹脂、アルキルフェノール樹脂、及び、芳香族系炭化水素樹脂からなる群より選択される少なくとも１種以上の樹脂を含有する、請求項１に記載の硬化性組成物。 The tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins, terpene-based resins, petroleum-based resins, alkylphenol resins, and aromatic hydrocarbon resins. Item 1. The curable composition according to item 1.
  3. 　重合体（ａ２）が、（メタ）アクリロイル基を分子内に１つより多く有するポリオキシアルキレン系重合体（ａ２″）である、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the polymer (a2) is a polyoxyalkylene polymer (a2″) having more than one (meth)acryloyl group in the molecule.
  4. 　重合体（ａ２）が、（メタ）アクリロイル基を分子内に１つより多く有する（メタ）アクリル酸エステル系重合体（ａ２′）である、請求項１又は２に記載の硬化性組成物。 3. The curable composition according to claim 1 or 2, wherein the polymer (a2) is a (meth)acrylate polymer (a2') having more than one (meth)acryloyl group in the molecule.
  5. 　重合体（ａ２）／メルカプト基を有する連鎖移動剤（ａ３）のモル比が０．０５以上である、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the molar ratio of polymer (a2)/chain transfer agent (a3) having a mercapto group is 0.05 or more.
  6. 　ホットメルト型硬化性組成物である、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, which is a hot-melt curable composition.
  7. 　粘着剤組成物である、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, which is an adhesive composition.
  8. 　前記粘着付与樹脂（Ｂ）が、ロジン系樹脂、及び、テルペン系樹脂からなる群より選択される少なくとも１種以上の樹脂を含有する、請求項７に記載の硬化性組成物。 The curable composition according to claim 7, wherein the tackifying resin (B) contains at least one resin selected from the group consisting of rosin-based resins and terpene-based resins.
  9. 　請求項１又は２に記載の硬化性組成物を硬化させて得られる硬化物。 A cured product obtained by curing the curable composition according to claim 1 or 2.
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Citations (6)

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WO2007023669A1 (en) * 2005-08-25 2007-03-01 Toagosei Co., Ltd. Curable resin compositions
JP2012122048A (en) * 2010-11-18 2012-06-28 Kaneka Corp Curable composition containing polyoxyalkylene-based polymer
JP2012122049A (en) * 2010-11-18 2012-06-28 Kaneka Corp Polyoxyalkylene-based polymer-containing curable composition
JP2012229310A (en) * 2011-04-25 2012-11-22 Kaneka Corp Curable composition containing (meth)acrylic polymer
WO2022009933A1 (en) * 2020-07-10 2022-01-13 株式会社カネカ (meth)acrylic acid ester-based copolymer and curable composition thereof
WO2022203065A1 (en) * 2021-03-26 2022-09-29 株式会社カネカ Curable composition and cured product thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007023669A1 (en) * 2005-08-25 2007-03-01 Toagosei Co., Ltd. Curable resin compositions
JP2012122048A (en) * 2010-11-18 2012-06-28 Kaneka Corp Curable composition containing polyoxyalkylene-based polymer
JP2012122049A (en) * 2010-11-18 2012-06-28 Kaneka Corp Polyoxyalkylene-based polymer-containing curable composition
JP2012229310A (en) * 2011-04-25 2012-11-22 Kaneka Corp Curable composition containing (meth)acrylic polymer
WO2022009933A1 (en) * 2020-07-10 2022-01-13 株式会社カネカ (meth)acrylic acid ester-based copolymer and curable composition thereof
WO2022203065A1 (en) * 2021-03-26 2022-09-29 株式会社カネカ Curable composition and cured product thereof

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