Sclerotic composition

Abstract

A multiple package-type curable composition comprises: an agent A that contains a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by general formula (1), an epoxy resin curing agent (D) having a tertiary amine, and an amine (E1) having an alicyclic structure; and an agent B that contains an epoxy resin (C). A multiple package-type curable composition comprises: an agent A that contains the aforesaid polymer (A), the aforesaid polymer (B) and an epoxy resin curing agent (D) having a tertiary amine; and an agent B that contains an epoxy resin (C), wherein the agent A and / or the agent B contain an amino alcohol compound (E2). General formula (1): -SiR5 cX3-c (in the formula, R5 represents an optionally substituted hydrocarbon group having 1-20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.)

Description

[Technical field]

[0001] The present invention relates to a multi-part curable composition. [Background technology]

[0002] In order to reduce weight, structural components in vehicles, aircraft, and railways are increasingly being replaced with lightweight materials other than steel, such as aluminum, magnesium, and carbon fiber composites, and multi-material construction is becoming more common, with multiple materials being used in one vehicle body. Since spot welding and laser welding can be difficult to use to join dissimilar materials, adhesive bonding using adhesives has attracted attention. Since steel plates, aluminum alloys, and fiber-reinforced composites each have a different linear expansion coefficient, the adhesive must be flexible enough to follow thermal distortion. For this reason, epoxy resins, which have high rigidity, can be disadvantageous, so a new structural adhesive with a high elastic modulus and flexibility is needed.

[0003] As an adhesive, a composition consisting of a reactive silicon group-containing polyoxyalkylene polymer and an epoxy resin, which has both high strength at break and flexibility, is known (see, for example, Patent Document 1). However, the strength of this composition is sometimes insufficient for use as an adhesive for structural components.

[0004] In contrast, Patent Document 2 discloses that a multi-component curable composition containing component A including a polyoxyalkylene polymer having more than one reactive silicon group at one end and a reactive silicon group-containing (meth)acrylic acid ester polymer, and component B including an epoxy resin, forms a cured product that exhibits high strength, high rigidity and flexibility, and can be used as a structural adhesive. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 02-214759 [Patent Document 2] International Publication No. 2019 / 069866 Summary of the Invention [Problem to be solved by the invention]

[0006] Generally, adhesives made of an organic polymer having a reactive silicon group and an epoxy resin undergo a long curing (aging) process lasting several days after bonding of the adherends, before they develop the desired physical properties.

[0007] However, structural adhesives may be used to bond adherends in a continuous line production system. In such cases, after bonding the adherends, a relatively short heating step is performed to semi-cure the structural adhesive before moving to the next step. At this time, the semi-cured structural adhesive is required to exhibit a certain degree of rigidity in order to ensure workability in the next step and subsequent steps.

[0008] The structural adhesive described in Patent Document 2 can produce a high-strength cured product after a long curing process, but the rigidity exhibited by a relatively short heating process does not reach a sufficient level, and there is a problem in that the rise in rigidity is slow.

[0009] In view of the above-mentioned current situation, an object of the present invention is to provide a curable composition that can exhibit high rigidity through a heating step of a relatively short time, and a cured product obtained by curing the composition. [Means for solving the problem]

[0010] Means for Solving the Problems The present inventors have conducted intensive research to find a solution to the above problems, and have discovered that the above problems can be solved by blending an amine or aminoalcohol compound having an alicyclic structure with a multi-component curable composition containing a reactive silicon group-containing polyoxyalkylene polymer, a reactive silicon group-containing (meth)acrylic acid ester polymer, and an epoxy resin, thereby completing the present invention.

[0011] That is, a first aspect of the present invention relates to a multi-component curable composition comprising a component A containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by general formula (1), an epoxy resin curing agent (D) having a tertiary amine other than an amine having an alicyclic structure, and an amine (E1) having an alicyclic structure, and a component B containing an epoxy resin (C). -SiR 5 c X 3-c (1) (In the formula, R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1. Preferably, the amine (E1) having an alicyclic structure is a compound in which an amino group is directly bonded to the alicyclic skeleton. A second aspect of the present invention relates to a multi-component curable composition comprising a component A containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by general formula (1), and an epoxy resin curing agent (D) having a tertiary amine other than an aminoalcohol compound, and a component B containing an epoxy resin (C), wherein either or both of the components A and B contain an aminoalcohol compound (E2). -SiR 5 c X 3-c (1) (In the formula, R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1. Preferably, the amino alcohol compound (E2) is an amino alcohol compound having no aromatic ring. Preferably, the amino alcohol compound (E2) is a trialcoholamine. In both of the above embodiments, the reactive silicon group of the polyoxyalkylene polymer (A) is preferably a trimethoxysilyl group. The reactive silicon group of the (meth)acrylic acid ester polymer (B) is preferably a trimethoxysilyl group. The terminal portion of the polyoxyalkylene polymer (A) is preferably a group represented by the general formula (2):

[0012] [ka]

[0013] (In the formula, R 1 ,R 3 are each independently a divalent linking group having 1 to 6 carbon atoms, R 1 ,R 3 The atom bonded to each carbon atom adjacent to R is either carbon, oxygen, or nitrogen. 2 ,R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 10. R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1. 1 CH 2 OCH 2 and R 3 CH 2 Preferably, R 2 and R 4 are each a hydrogen atom. Preferably, the (meth)acrylic acid ester polymer (B) is a polymer having, as constituent monomers, a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer (b2) which is a (meth)acrylic acid ester polymer having a polymerizable unsaturated group.

[0014] The present invention also relates to a structural adhesive comprising the multi-component curable composition, and further to a cured product obtained by curing the multi-component curable composition. Effect of the Invention

[0015] According to the present invention, it is possible to provide a curable composition that can exhibit high rigidity through a heating step for a relatively short time, and a cured product obtained by curing the composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The following describes the embodiments of the present invention in detail, but the present invention is not limited to these embodiments.

[0017] A first aspect of the present invention is a multi-component curable composition comprising a component A containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by the following general formula (1), an epoxy resin curing agent (D) having a tertiary amine other than an amine having an alicyclic structure, and an amine (E1) having an alicyclic structure, and a component B containing an epoxy resin (C).

[0018] A second aspect of the present invention is a multi-component curable composition comprising an A component containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by the following general formula (1), and an epoxy resin curing agent (D) having a tertiary amine other than an aminoalcohol compound, and a B component containing an epoxy resin (C), wherein either or both of the A component and the B component contain an aminoalcohol compound (E2).

[0019] <<Polyoxyalkylene polymer (A) having reactive silicon group>> <Reactive silicon group> The polyoxyalkylene polymer (A) has a reactive silicon group represented by general formula (1). -SiR 5 c X 3-c (1) (In the formula, R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1.

[0020] R 5 The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. 5 Specific examples of the alkyl group include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group. Preferred are a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group, and more preferred are a methyl group and a methoxymethyl group.

[0021] Examples of X include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred, since they are mildly hydrolyzable and easy to handle, and a methoxy group and an ethoxy group are particularly preferred.

[0022] Specific examples of the reactive silicon group contained in the polyoxyalkylene polymer (A) include, but are not limited to, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, and a (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred because they exhibit high activity and give cured products having good mechanical properties, and the trimethoxysilyl group and triethoxysilyl group are more preferred, with the trimethoxysilyl group being even more preferred, because they give cured products with high rigidity.

[0023] The polyoxyalkylene polymer (A) may have more than one reactive silicon group on average at one terminal site. Having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) contains a polyoxyalkylene having two or more reactive silicon groups at one terminal site as shown in the following general formula (2). That is, the polyoxyalkylene polymer (A) may contain only a polyoxyalkylene having two or more reactive silicon groups at one terminal site, or may contain both a polyoxyalkylene having two or more reactive silicon groups at one terminal site and a polyoxyalkylene having one reactive silicon group at one terminal site. In addition, the multiple terminal sites of one polyoxyalkylene molecule may include both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group. Furthermore, the polyoxyalkylene polymer (A) as a whole has, on average, more than one reactive silicon group at one terminal site, but may contain a polyoxyalkylene having a terminal site that does not have a reactive silicon group.

[0024] [ka]

[0025] (In the formula, R 1 ,R 3 are each independently a divalent linking group having 1 to 6 carbon atoms, R 1 ,R 3 The atom bonded to each carbon atom adjacent to R is either carbon, oxygen, or nitrogen. 2 ,R 4 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 10. R 5 , X, and c are as described above for formula (1).

[0026] R 1 , R 3R may be a divalent organic group having 1 to 6 carbon atoms, or a hydrocarbon group which may contain an oxygen atom. The number of carbon atoms in the hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. 1 Specific examples of the 2 OCH 2 , C.H. 2 O, C.H. 2 However, preferably, CH 2 OCH 2 R 3 Specific examples of the 2 , C.H. 2 CH 2 However, preferably, CH 2 It is.

[0027] R 2 , R 4 The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. 2 , R 4 Specific examples of the alkyl group include a hydrogen atom, a methyl group, and an ethyl group, with a hydrogen atom and a methyl group being preferred, and a hydrogen atom being more preferred.

[0028] In a particularly preferred embodiment, the terminal moiety represented by the general formula (2) is R 1 CH 2 OCH 2 and R 3 CH 2 and R 2 and R 4 are each a hydrogen atom. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and further preferably 1 or 2. However, n is not limited to a single value, and may be a mixture of multiple values.

[0029] The polyoxyalkylene polymer (A) preferably has more than 1.0 reactive silicon group on average at one terminal site, more preferably 1.1 or more, even more preferably 1.5 or more, and even more preferably 2.0 or more, and preferably 5 or less, and more preferably 3 or less.

[0030] The number of terminal moieties having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A) is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 1.1 or more, and even more preferably 1.5 or more on average, and is preferably 4 or less, and more preferably 3 or less.

[0031] The polyoxyalkylene polymer (A) may have reactive silicon groups in positions other than the terminal positions, but it is preferable for them to be present only in the terminal positions, since this makes it easier to obtain a rubber-like cured product that has high elongation and a low elastic modulus.

[0032] The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, even more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. Also, it is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. If the average number of reactive silicon groups per molecule is 1.0 or less, it may not be possible to obtain a cured product with high strength. If the average number of reactive silicon groups per molecule is more than 6.0, it may not be possible to obtain a cured product with high elongation.

[0033] <Main chain structure> The main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Among these, polyoxypropylene is preferred.

[0034] The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, in terms of polystyrene equivalent molecular weight measured by GPC. If the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may be disadvantageous in terms of production costs, while if it exceeds 100,000, the viscosity becomes high, which tends to be disadvantageous in terms of workability.

[0035] The molecular weight of the polyoxyalkylene polymer (A) can also be expressed as an end-group-converted molecular weight obtained by directly measuring the end-group concentration of an organic polymer precursor before the introduction of reactive silicon groups by titration analysis based on the principles of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The end-group-converted molecular weight of the polyoxyalkylene polymer (A) can also be obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight obtained by GPC of the polyoxyalkylene polymer (A) into an end-group-converted molecular weight.

[0036] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, specifically, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. From the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0037] The main chain structure of the polyoxyalkylene polymer (A) may be either linear or branched.

[0038] <Method for synthesizing polyoxyalkylene polymer (A)> Next, a method for synthesizing the polyoxyalkylene polymer (A) will be described. The polyoxyalkylene polymer (A) having more than 1.0 reactive silicon group on average at one terminal site, which is a preferred embodiment, is preferably obtained by introducing two or more carbon-carbon unsaturated bonds into one terminal of a hydroxyl group-terminated polymer obtained by polymerization, and then reacting the polymer with a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bond. The above-mentioned preferred synthesis method will be described below.

[0039] (polymerization) The polyoxyalkylene polymer (A) is preferably produced by a method in which an epoxy compound is polymerized with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex.

[0040] Examples of initiators having a hydroxyl group include those having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polyoxypropylene monoallyl ether, and polyoxypropylene monoalkyl ether.

[0041] Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether, etc. Among these, propylene oxide is preferred.

[0042] (Introduction of carbon-carbon unsaturated bonds) A preferred method for introducing two or more carbon-carbon unsaturated bonds into one terminal is to react an alkali metal salt with a hydroxyl-terminated polymer, then react it with an epoxy compound having a carbon-carbon unsaturated bond, and then react it with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond. By using this method, it is possible to efficiently and stably introduce reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain by the polymerization conditions.

[0043] As the alkali metal salt, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium methoxide are more preferred. In terms of availability, sodium methoxide is particularly preferred.

[0044] The temperature when reacting with the alkali metal salt is preferably from 50° C. to 150° C., more preferably from 110° C. to 140° C. The time when reacting with the alkali metal salt is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

[0045] As the epoxy compound having a carbon-carbon unsaturated bond, in particular, a compound represented by the general formula (3):

[0046] [ka]

[0047] (R in the formula 1 , R 2is the same as above.) can be preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

[0048] The amount of the epoxy compound having a carbon-carbon unsaturated bond added can be any amount taking into consideration the amount of carbon-carbon unsaturated bonds introduced into the polymer and the reactivity. In particular, the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.2 or more, more preferably 0.5 or more. Also, it is preferably 5.0 or less, more preferably 2.0 or less.

[0049] The reaction temperature when the epoxy compound having a carbon-carbon unsaturated bond is subjected to a ring-opening addition reaction with the polymer containing a hydroxyl group is preferably 60°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower.

[0050] Examples of halogenated hydrocarbon compounds having a carbon-carbon unsaturated bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Of these, it is more preferable to use allyl chloride and methallyl chloride because of their ease of handling.

[0051] The amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond added is not particularly limited, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.7 or more, more preferably 1.0 or more, and is preferably 5.0 or less, more preferably 2.0 or less.

[0052] The temperature at which the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferably from 50° C. to 150° C., more preferably from 110° C. to 140° C. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

[0053] (Introduction of reactive silicon groups) The method for introducing the reactive silicon group is not particularly limited, and any known method can be used. The following are examples of the introduction method. (i) A method in which a hydrosilane compound is added to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction. (ii) A method of reacting a polymer having a carbon-carbon unsaturated bond with a compound (also called a silane coupling agent) having both a group capable of reacting with the carbon-carbon unsaturated bond to form a bond and a reactive silicon group. Examples of the group capable of reacting with the carbon-carbon unsaturated bond to form a bond include, but are not limited to, a mercapto group. (iii) A method of reacting a reactive group-containing polymer with a silane coupling agent. Combinations of reactive groups of the reactive group-containing polymer and the silane coupling agent include, but are not limited to, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, an amino group and an α,β-unsaturated carbonyl group (reaction by Michael addition), a carboxyl group and an epoxy group, an unsaturated bond and a mercapto group, and the like.

[0054] Method (i) is preferred because the reaction is simple, the amount of reactive silicon group introduced can be adjusted, and the physical properties of the resulting reactive silicon group-containing polyoxyalkylene polymer (A) are stable. Methods (ii) and (iii) are preferred because they have a wide range of reaction options and can easily increase the rate of reactive silicon group introduction.

[0055] The hydrosilane compound that can be used in the method (i) is not particularly limited, and examples thereof include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, and (N,N-diethylaminomethyl)diethoxysilane.

[0056] The amount of the hydrosilane compound used, in terms of a molar ratio to the carbon-carbon unsaturated bonds in the precursor polymer (molar number of hydrosilane / molar number of carbon-carbon unsaturated bonds), is preferably 0.05 to 10 from the viewpoint of reactivity, and more preferably 0.3 to 2 from the viewpoint of economy.

[0057] The hydrosilylation reaction is accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, etc. may be used. For example, platinum supported on a support such as alumina, silica, or carbon black, chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [e.g., Pt(CH 2 =CH 2 ) 2 (PPh 3 ), Pt(CH 2 =CH 2 ) 2 Cl 2 ]; platinum-vinylsiloxane complex [Pt{(vinyl)Me 2 SiOSiMe 2 (vinyl)}, Pt{Me(vinyl)SiO} 4 ]; Platinum-phosphine complex [Ph(PPh 3 ) 4 , Pt(PBu 3 ) 4 ]; platinum-phosphite complex [Pt{P(OPh) 3} 4From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0058] Examples of silane coupling agents that can be used in the above method (ii) or (iii) include mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, and mercaptomethyldimethoxymethylsilane, which react with unsaturated bonds; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, and isocyanate propyldimethoxymethylsilane, which react with hydroxyl groups; isocyanate silanes such as isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, isocyanate methyl dimethoxy methyl silane; epoxy silanes such as 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl dimethoxy methyl silane, 3-glycidoxypropyl triethoxy silane, glycidoxymethyl trimethoxy silane, glycidoxymethyl triethoxy silane, glycidoxymethyl dimethoxy methyl silane which react with hydroxyl groups, amino groups or carboxy groups; Reacts with propyl groups, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2-aminoethyl)propyldimethoxymethylsilane, 3-(2-aminoethyl)propyltriethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzene Examples of aminosilanes include N-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(3-(trimethoxysilyl)propyl)amine; and hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane.

[0059] The main chain of the polyoxyalkylene polymer (A) may contain an ester bond or a bond represented by the general formula (4): -NR 6 -C(=O)- (4) (In the formula, R 6 represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

[0060] A cured product obtained from a curable composition containing a polyoxyalkylene polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds. However, the polyoxyalkylene polymer (A) containing an amide segment or the like may be cleaved by heat or the like. In addition, the curable composition containing a polyoxyalkylene polymer (A) containing an amide segment or the like tends to have a high viscosity. In consideration of the above-mentioned advantages and disadvantages, a polyoxyalkylene containing an amide segment or the like may be used as the polyoxyalkylene polymer (A), or a polyoxyalkylene not containing an amide segment or the like may be used.

[0061] Examples of the amide segment represented by the general formula (4) include those formed by a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, a reaction between an isocyanate group and a mercapto group, etc. In addition, those formed by a reaction between the amide segment containing an active hydrogen atom and an isocyanate group are also included in the amide segment represented by the general formula (4).

[0062] The polyoxyalkylene polymer (A) containing an amide segment can be produced, for example, by reacting a polyoxyalkylene having an active hydrogen-containing group at its terminal with an excess of a polyisocyanate compound to synthesize a polymer having an isocyanate group at its terminal, and then, or simultaneously with the synthesis of the polymer, reacting a polyoxyalkylene having an active hydrogen-containing group at its terminal with a polyisocyanate compound represented by the general formula (5): ZR 7-SiR 5 c X 3-c (5) (In the formula, R 5 , X and c are the same as above. 7 is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group.) can be reacted with all or a part of the isocyanate groups of the synthesized polymer.

[0063] The silicon compound represented by the general formula (5) is not particularly limited, and examples thereof include amino group-containing silanes such as γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, and N-ethylaminoisobutyltrimethoxysilane; hydroxyl group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; and the like. In addition, as described in JP-A-6-211879 (U.S. Patent No. 5,364,955), JP-A-10-53637 (U.S. Patent No. 5,756,751), JP-A-10-204144 (EP0831108), JP-A-2000-169544, and JP-A-2000-169545, Michael addition reaction products of various α,β-unsaturated carbonyl compounds and primary amino group-containing silanes, or Michael addition reaction products of various (meth)acryloyl group-containing silanes and primary amino group-containing compounds can also be used as the silicon compound represented by the general formula (5).

[0064] As a method for producing the polyoxyalkylene polymer (A) containing an amide segment, for example, a method is carried out by reacting a polyoxyalkylene having an active hydrogen-containing group at its terminal with a compound represented by the general formula (6): O=C=NR 7 -SiR 5c X 3-c (6) (In the formula, R 7 , R 5 , X and c are the same as defined above.

[0065] The reactive silicon group-containing isocyanate compound represented by the general formula (6) is not particularly limited, and examples thereof include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, γ-(methoxymethyl)dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl)dimethoxysilylmethyl isocyanate, and the like.

[0066] When the polyoxyalkylene polymer (A) contains an amide segment, the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, more preferably 1.5 to 5, and particularly preferably 2 to 3. If this number is less than 1, the curability may be insufficient, and conversely, if it is greater than 10, the polyoxyalkylene polymer (A) may become highly viscous and difficult to handle. In order to reduce the viscosity of the curable composition and improve workability, it is preferable that the polyoxyalkylene polymer (A) does not contain an amide segment.

[0067] <<Reactive silicon group-containing (meth)acrylic acid ester polymer (B)>> The (meth)acrylic acid ester monomer constituting the main chain of the reactive silicon group-containing (meth)acrylic acid ester polymer (B) (also referred to as "(meth)acrylic acid ester polymer (B)") is not particularly limited, and various monomers can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonaphthalene (meth)acrylate, methyl methacrylate, ethyl meth ... methacrylate, n-butyl (meth)acrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonaphthalene (meth)acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, nyl, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethyl)propyl (meth)acrylate Examples of (meth)acrylic acid monomers include (meth)acrylic acid (2-trimethoxysilyl)propyl, (meth)acrylic acid (2-trimethoxysilyl)ethyl, (meth)acrylic acid (2-dimethoxymethylsilyl)ethyl, (meth)acrylic acid trimethoxysilylmethyl, (meth)acrylic acid (dimethoxymethylsilyl)methyl, (meth)acrylic acid ethylene oxide adducts, (meth)acrylic acid trifluoromethylmethyl, (meth)acrylic acid 2-trifluoromethylethyl, (meth)acrylic acid 2-perfluoroethylethyl, (meth)acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth)acrylic acid perfluoroethyl, (meth)acrylic acid trifluoromethyl, (meth)acrylic acid bis(trifluoromethyl)methyl, (meth)acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth)acrylic acid 2-perfluorohexylethyl, (meth)acrylic acid 2-perfluorodecylethyl, and (meth)acrylic acid 2-perfluorohexadecylethyl.

[0068] Examples of monomer units other than those mentioned above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylol acrylamide and N-methylol methacrylamide; monomers containing an epoxy group such as glycidyl acrylate and glycidyl methacrylate; and monomers containing a nitrogen-containing group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

[0069] The (meth)acrylic acid ester polymer (B) may be a polymer obtained by copolymerizing a (meth)acrylic acid ester monomer with a vinyl monomer copolymerizable therewith. The vinyl monomer is not particularly limited, and examples thereof include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octyl ... Examples of the monomers include maleimide monomers such as dimaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol, and it is also possible to use a plurality of these as copolymerization components.

[0070] Among the (meth)acrylic acid ester-based polymers obtained from the above-mentioned monomers, copolymers composed of (meth)acrylic acid ester-based monomers and, in some cases, styrene-based monomers are preferred due to their excellent physical properties, (meth)acrylic acid ester-based polymers composed of acrylic acid ester monomers and methacrylic acid ester monomers are more preferred, and acrylic acid ester-based polymers composed of acrylic acid ester monomers are particularly preferred.

[0071] The (meth)acrylic acid ester polymer (B) has a reactive silicon group represented by the above-mentioned general formula (1). The reactive silicon group of the (meth)acrylic acid ester polymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene polymer (A). R 5 Specific examples of the alkyl group include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group, with a methyl group and an ethyl group being preferred.

[0072] Examples of X include a hydroxyl group, hydrogen, halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred because they are mildly hydrolyzable and easy to handle, and a methoxy group and an ethoxy group are particularly preferred.

[0073] Specific examples of the reactive silicon group contained in the (meth)acrylic acid ester polymer (B) include, but are not limited to, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, and a (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred because they exhibit high activity and give cured products with good mechanical properties, and the trimethoxysilyl group and triethoxysilyl group are more preferred, with the trimethoxysilyl group being even more preferred, because they give cured products with a high Young's modulus.

[0074] The reactive silicon group equivalent of the (meth)acrylic acid ester polymer (B) is not particularly limited, but is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, and even more preferably 0.6 mmol / g or more. The reactive silicon group equivalent is preferably 2.0 mmol / g or less, and more preferably 1.0 mmol / g or less in terms of suppressing the decrease in elongation of the cured product. In addition, in order to obtain a cured product with high Young's modulus and high rigidity, the reactive silicon group equivalent is particularly preferably 0.6 mmol / g or more and 1.0 mmol / g or less.

[0075] The method for introducing a reactive silicon group into a (meth)acrylic acid ester polymer is not particularly limited, and for example, the following methods can be used. (iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group with the above-mentioned monomer, in which the reactive silicon groups tend to be randomly introduced into the main chain of the polymer. (v) A method of polymerizing a (meth)acrylic acid ester polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent, which can introduce a reactive silicon group into the polymer terminal. (vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (V group), and then reacting with a compound having a reactive silicon group and a functional group reactive with the V group. Specific examples include a method of copolymerizing 2-hydroxyethyl acrylate, and then reacting with an isocyanate silane having a reactive silicon-containing group, and a method of copolymerizing glycidyl acrylate, and then reacting with an aminosilane compound having a reactive silicon-containing group. (vii) A method of modifying the terminal functional groups of a (meth)acrylic acid ester polymer synthesized by a living radical polymerization method to introduce reactive silicon groups. A (meth)acrylic acid ester polymer obtained by a living radical polymerization method has a terminal functional group that can be easily introduced, and by modifying the polymer, reactive silicon groups can be introduced to the terminals of the polymer.

[0076] Examples of silicon compounds that can be used to introduce reactive silicon groups into the (meth)acrylic acid ester polymer (B) using the above method include the following compounds. Compounds having a polymerizable unsaturated group and a reactive silicon-containing group used in method (iv) include 3-(dimethoxymethylsilyl)propyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (trimethoxysilyl)methyl (meth)acrylate, (triethoxysilyl)methyl (meth)acrylate, and 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate. From the viewpoint of availability, 3-(dimethoxymethylsilyl)propyl (meth)acrylate and 3-(trimethoxysilyl)propyl (meth)acrylate are particularly preferred.

[0077] Examples of the mercaptosilane compound having a reactive silicon-containing group used in the method (v) include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, and (mercaptomethyl)trimethoxysilane.

[0078] Examples of the compound having a reactive silicon group and a functional group reactive with the V group to be used in the method (vi) include isocyanate silane compounds such as 3-isocyanate propyl dimethoxymethyl silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl dimethoxymethyl silane, isocyanate methyl trimethoxy silane, and isocyanate methyl triethoxy silane; 3-glycidoxypropyl dimethoxymethyl silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, and glycidoxy methyl Epoxy silane compounds such as trimethoxysilane, glycidoxymethyl dimethoxymethyl silane, and glycidoxymethyl triethoxysilane; and aminosilane compounds such as 3-aminopropyl dimethoxymethyl silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, aminomethyl dimethoxymethyl silane, aminomethyl trimethoxysilane, aminomethyl triethoxysilane, N-cyclohexyl aminomethyl dimethoxymethyl silane, N-cyclohexyl aminomethyl trimethoxysilane, and N-cyclohexyl aminomethyl triethoxysilane.

[0079] In the method (vii), any modification reaction can be used. For example, a method using a compound having a reactive silicon group and a functional group capable of reacting with the terminal reactive group obtained by polymerization, or a method using a compound having a double bond and a functional group capable of reacting with the terminal reactive group to introduce a double bond into the polymer terminal, and then introducing a reactive silicon group therein by hydrosilylation or the like can be used.

[0080] These methods may be used in any combination. For example, by combining method (vi) and method (v), it is possible to obtain a (meth)acrylic acid ester polymer (B) having reactive silicon groups at both the molecular chain terminals and / or side chains.

[0081] The (meth)acrylic acid ester polymer (B) preferably contains a polymer containing 40% by weight or more of all monomers of alkyl (meth)acrylates whose alkyl carbon number is 1 to 3, in order to provide high rigidity. The (meth)acrylic acid ester polymer (B) may be composed only of a polymer containing 40% by weight or more of all monomers of alkyl (meth)acrylates whose alkyl carbon number is 1 to 3, but it is preferable that the (meth)acrylic acid ester polymer (B) contains, together with the polymer, a polymer containing 40% by weight or more of all monomers of alkyl (meth)acrylates whose alkyl carbon number is 4 to 30, in order to provide improved rigidity, elongation, and strength, by blending both of them.

[0082] In addition, the (meth)acrylic acid ester polymer (B) preferably contains a polymer obtained by copolymerizing a monomer mixture containing 40% by weight or more of alkyl (meth)acrylate having an alkyl carbon number of 1 to 3, based on all monomers, and 40% by weight or more of alkyl (meth)acrylate having an alkyl carbon number of 4 to 30, based on all monomers, because this improves rigidity, elongation, and strength.

[0083] Next, a (meth)acrylic acid ester-based polymer (B) polymerized using a macromonomer, which is one of the preferred embodiments of the (meth)acrylic acid ester-based polymer (B), will be described.

[0084] The (meth)acrylic acid ester polymer (B) polymerized using a macromonomer is a polymer having as constituent monomers the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group represented by the above general formula (1), and the macromonomer (b2) which is a (meth)acrylic acid ester polymer having a polymerizable unsaturated group. The polymer may further have as a constituent monomer a (meth)acrylic acid alkyl ester (b3) having an alkyl carbon number of 1 to 3. In this application, "(meth)acrylic" means "acrylic and / or methacrylic".

[0085] (Monomer (b1) having a reactive silicon group and a polymerizable unsaturated group) Examples of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group include compounds having a (meth)acryloxy group and a reactive silicon group, such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; compounds having a vinyl group and a reactive silicon group, such as vinyltrimethoxysilane and vinyltriethoxysilane. These compounds may be used alone or in combination of two or more.

[0086] The total content of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight, and even more preferably from 1 to 20% by weight, based on all the monomers constituting the (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2).

[0087] (Macromonomer (b2)) The macromonomer (b2) is a (meth)acrylic acid ester-based polymer having a polymerizable unsaturated group. The macromonomer (b2) is itself a polymer, but can be copolymerized with the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group by the polymerizable unsaturated group, and is a monomer that constitutes the (meth)acrylic acid ester-based polymer (B).

[0088] The main chain skeleton of the macromonomer (b2) is a (meth)acrylic acid ester polymer. The monomer constituting the main chain skeleton of the macromonomer (b2) is not particularly limited, and various monomers can be used. Examples of the (meth)acrylic monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , ethylene oxide adducts of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, 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-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and 2-aminoethyl (meth)acrylate.

[0089] Furthermore, other monomers copolymerizable with the above (meth)acrylic monomers may be used. Examples of other monomers include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl esters, and maleic acid dialkyl esters; fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl esters, and fumaric acid dialkyl esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, and heptanediol. Examples of the monomer include maleimide monomers such as xylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; olefin monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; (meth)acrylamide; (meth)acrylonitrile; and vinyl monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. Only one type of other monomer may be used, or two or more types may be used in combination.

[0090] The macromonomer (b2) has a polymerizable unsaturated group, which allows it to exhibit polymerizability. In the macromonomer (b2), the polymerizable unsaturated group may be introduced either at the molecular chain terminal or at the side chain of the (meth)acrylic acid ester polymer, but is preferably introduced at the molecular chain terminal from the viewpoint of adhesiveness.

[0091] The polymerizable unsaturated group of the macromonomer (b2) is not particularly limited as long as it is an unsaturated group that exhibits polymerizability in a general radical polymerization method, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a methallyl group, etc. Acryloyl groups and methacryloyl groups are preferred because they exhibit good polymerizability.

[0092] The method for introducing a polymerizable unsaturated group into the macromonomer (b2) is not particularly limited, and for example, the following methods (viii) to (x) can be used. (viii) A method of copolymerizing a monomer having two types of polymerizable unsaturated groups having different reactivities (such as allyl acrylate) together with a monomer having a (meth)acrylic structure. (ix) A method in which a compound having a polymerizable unsaturated group and a reactive functional group (Z group) (e.g., acrylic acid, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth)acrylic structure, and then a compound having a polymerizable unsaturated group and a functional group reactive with the Z group (e.g., diethyl isocyanate (meth)acrylate, etc.) is reacted with the copolymer. (x) A method in which a monomer having a (meth)acrylic structure is polymerized by living radical polymerization, and then a polymerizable unsaturated group is introduced into the molecular chain terminal.

[0093] These methods may be used in any combination. Among these methods, it is preferable to use method (x) since it is possible to introduce a polymerizable unsaturated group to the molecular chain end. Examples of the "living radical polymerization method" include a method using a cobalt porphyrin complex as shown in Journal of American Chemical Society (J.Am.Chem.Soc.), 1994, vol. 116, p. 7943, a method using a nitroxide radical as shown in JP-A-2003-500378, and an atom transfer radical polymerization (ATRP) method using an organic halide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst as shown in JP-A-11-130931. The atom transfer radical polymerization method is the most preferable since it is easy to introduce a polymerizable unsaturated group to the end.

[0094] It is also possible to use 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 described in JP-A-2001-040037.

[0095] The polymerizable unsaturated group contained in the macromonomer (b2) preferably has a structure represented by the following general formula (7). CH 2 =C(R 8 )-COO-Z (7) (In the formula, R 8 represents hydrogen or a methyl group. Z represents the main chain skeleton of the macromonomer (b2).

[0096] The number average molecular weight of the macromonomer (b2) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 30,000 or less. If the number average molecular weight of the macromonomer (b2) is small, the viscosity of the (meth)acrylic acid ester polymer (B) is low, but good adhesiveness tends not to be obtained. On the other hand, if the number average molecular weight of the macromonomer (b2) is too large, the viscosity tends to be too high, making handling difficult.

[0097] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the macromonomer (b2) is not particularly limited, but is preferably narrow, more preferably less than 2.0, even more preferably 1.6 or less, particularly preferably 1.5 or less, more particularly preferably 1.4 or less, even more particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0098] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the macromonomer (b2) are values ​​measured by GPC (polystyrene equivalent), and the detailed measurement method will be described in the Examples.

[0099] The (meth)acrylic acid ester polymer (B) is composed of the macromonomer (b2) and other monomers, and the main chain of the (meth)acrylic acid ester polymer (B) is called the backbone chain, and the polymer chain branched from the backbone chain, which is derived from the macromonomer (b2), is called the branch chain. The monomers constituting the backbone and the branch chain are composed of the above-mentioned monomers and are not particularly limited. Since good adhesion can be obtained, it is preferable that the Tg of the branch chain is lower than that of the backbone chain.

[0100] The Tg of the backbone is preferably from -60°C to 150°C, more preferably from 0°C to 130°C, and further preferably from 30°C to 100°C.

[0101] The Tg of the branched chain is preferably −100° C. to 150° C., more preferably −90° C. to 100° C., and further preferably −80° C. to 50° C. Tg is calculated by the following Fox formula. Fox formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of monomer i.)

[0102] The glass transition temperature of homopolymers is based on the glass transition temperature (Tg) described in POLYMER HANDBOOK-FOURTH EDITION- (J. Brandrup et al.). When calculating Tg using the Fox formula, the calculation does not include monomers having reactive silicon groups.

[0103] The total content of the macromonomer (b2) is preferably from 1 to 50% by weight, more preferably from 5 to 40% by weight, and even more preferably from 10 to 30% by weight, based on all the monomers constituting the (meth)acrylic acid ester polymer (B).

[0104] The macromonomer (b2) may be introduced into either the molecular chain terminal or the side chain of the (meth)acrylic acid ester polymer (B), but is preferably introduced into the side chain from the viewpoint of adhesiveness. The number of macromonomers contained in one molecule of the (meth)acrylic acid ester polymer (B) is, on average, preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.3 or less.

[0105] ((Meth)acrylic acid alkyl ester (b3)) The alkyl group constituting the (meth)acrylic acid alkyl ester (b3) has a carbon number of 1 to 3. Specific examples of the (b3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. These may be used alone or in combination of two or more.

[0106] From the viewpoint of achieving both flexibility and high rigidity, the total content of the (meth)acrylic acid alkyl ester (b3) is preferably 40% by weight or more, more preferably 45% by weight or more, even more preferably 50% by weight or more, even more preferably 55% by weight or more, and even more preferably 60% by weight or more, based on the total monomers constituting the (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2). Also, from the viewpoint of durable adhesion, the total content of the (meth)acrylic acid ester polymer (B) is preferably 50% by weight or more, more preferably 55% by weight or more, and even more preferably 60% by weight or more. In order to ensure compatibility with the polyoxyalkylene polymer (A), the total content is preferably 70% by weight or less, and more preferably 65% ​​by weight or less.

[0107] The (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2) is a polymer having at least the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and the macromonomer (b2) as constituent monomers, but may contain a (meth)acrylic acid alkyl ester (b3) having an alkyl carbon number of 1 to 3, or other monomers as constituent monomers. Examples of such monomers include (meth)acrylic monomers that do not fall under (b1) to (b3) and other monomers other than (meth)acrylic monomers, and specifically, the various monomers exemplified for the macromonomer (b2) above can be used.

[0108] The (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2) is synthesized by copolymerizing the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group with another monomer. This allows the reactive silicon group to be randomly introduced into the main chain of the polymer. However, in order to further introduce a reactive silicon group into the (meth)acrylic acid ester polymer (B), the above-mentioned method can also be used in combination.

[0109] The monomer composition of the (meth)acrylic acid ester polymer (B) can be selected depending on the application and purpose, and in applications requiring strength, it is preferable for the polymer to have a relatively high glass transition temperature (Tg), preferably 0° C. or higher and 200° C. or lower, and more preferably 20° C. or higher and 100° C. or lower. Tg is calculated by the above-mentioned Fox formula.

[0110] The number average molecular weight of the (meth)acrylic acid ester polymer (B) is not particularly limited, but is preferably from 500 to 50,000, more preferably from 500 to 30,000, and particularly preferably from 1,000 to 10,000, in terms of polystyrene equivalent molecular weight measured by GPC. In particular, the number average molecular weight of the (meth)acrylic acid ester polymer (B) is preferably 3,000 or less, since good adhesiveness is exhibited even after a moist heat resistance test.

[0111] Methods of blending a (meth)acrylic acid ester polymer (B) with a polyoxyalkylene polymer (A) have been proposed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc. In addition, a method of polymerizing a (meth)acrylic acid ester monomer in the presence of a polyoxypropylene polymer having a reactive silicon group can be used.

[0112] The weight ratio (A):(B) of the polyoxyalkylene polymer (A) to the (meth)acrylic acid ester polymer (B) is preferably 95:5 to 50:50, that is, the proportion of (A) is 50% 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, in terms of achieving both high rigidity and flexibility, (A):(B) is preferably 80:20 to 50:50, more preferably 70:30 to 50:50.

[0113] <<Epoxy resin (C)>> Examples of the epoxy resin (C) include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, and glycidyl ether of tetrabromobisphenol A, novolac type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, and epoxidized products of unsaturated polymers such as petroleum resins, but are not limited thereto. Generally used epoxy resins can be used. Epoxy resins having at least two epoxy groups per molecule are preferred because they have high reactivity during curing and the cured product easily forms a three-dimensional network. More preferred examples include bisphenol A type epoxy resins and novolac type epoxy resins.

[0114] The epoxy resin (C) is preferably used in such an amount that the weight ratio [(A+B):(C)] of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) to the epoxy resin (C) is 90:10 to 50:50, that is, the ratio of (A+B) is 50% by weight or more and 90% by weight or less. If the ratio of (A+B) is more than 90% by weight, the strength decreases, and if it is less than 50% by weight, the flexibility decreases and the composition becomes too hard. Furthermore, 80:20 to 60:40 is more preferable in terms of the balance between flexibility and strength.

[0115] Young's modulus is an index of rigidity, and the Young's modulus of the cured product obtained by curing the curable composition according to this embodiment can be adjusted as desired by adjusting the weight ratio of the polyoxyalkylene polymer (A), the (meth)acrylic acid ester polymer (B), and the epoxy resin (C) specified in the present application. For example, in order to obtain a cured product having a Young's modulus of less than 100 MPa measured at 23° C., it is preferable that (A):(B) is 95:5 to 60:40 and (A+B):(C) is 90:10 to 60:40.

[0116] In order to obtain a cured product having a Young's modulus of 100 MPa or more when measured at 23° C., it is preferable that (A):(B) is 80:20 to 50:50 and (A+B):(C) is 80:20 to 50:50.

[0117] <<Epoxy resin curing agent having tertiary amine (D)>> As the epoxy resin curing agent (D) for curing the epoxy resin (C), it is preferable to use an epoxy resin curing agent having a tertiary amine. By using the epoxy resin curing agent (D) having a tertiary amine, a cured product having high rigidity, high strength, and high elongation can be obtained. However, in the first embodiment, the epoxy resin curing agent is a compound that does not fall under the amine having an alicyclic structure described later. In the second embodiment, the epoxy resin curing agent is a compound that does not fall under the amino alcohol compound described later. The tertiary amine in the second embodiment does not have an alcoholic hydroxyl group, but may have a phenolic hydroxyl group.

[0118] As the epoxy resin curing agent (D) having a tertiary amine, any compound having a tertiary amine can be used. Specifically, for example, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,6-diaminohexane, N,N-dimethylbenzylamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, 2,4,6-tris(dimethylaminomethyl)phenol, tripropylamine, DBU, DBN, and salts of these tertiary amines can be exemplified, but are not limited to these. In addition, two or more kinds may be used in combination, and a known epoxy resin curing agent other than the component (D) may be further added.

[0119] The epoxy resin curing agent (D) having a tertiary amine is preferably an aromatic amine, more preferably having three or more amino groups, and specifically, 2,4,6-tris(dimethylaminomethyl)phenol can be exemplified.

[0120] The amount of the epoxy resin curing agent (D) used is preferably 0.1 parts by weight or more and 50 parts by weight or less, more preferably 0.1 parts by weight or more and 40 parts by weight or less, and even more preferably 0.5 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the epoxy resin (C).

[0121] <<Amine with an Alicyclic Structure (E1)>> The amine (E1) having an alicyclic structure used in the first embodiment is an organic compound having an amino group and an alicyclic structure. By incorporating this compound, the curable composition according to the first embodiment can exhibit a relatively high rigidity by a heating step for a relatively short time.

[0122] As the amine (E1) having an alicyclic structure, an amine having an alicyclic structure and not having an aromatic group or a heterocyclic group is preferred. In addition, as the amine (E1) having an alicyclic structure, those corresponding to the epoxy resin curing agent (D) having a tertiary amine described above are excluded. Therefore, as the amine (E1) having an alicyclic structure, a primary amine or a secondary amine having an alicyclic structure is preferred. Furthermore, as the amine (E1) having an alicyclic structure, a compound in which an amino group is directly bonded to an alicyclic skeleton is particularly preferred, since it has a high effect of exhibiting rigidity by a short-time heating process.

[0123] The alicyclic structure of the amine (E1) is not particularly limited, and may be either saturated or unsaturated, and may be either monocyclic, bicyclic or polycyclic. Specific examples of the alicyclic structure include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0124] Specific examples of the amine (E1) having an alicyclic structure include, but are not limited to, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexanamine), cyclohexylamine, dicyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, norbornenediamine, 1,2-diaminocyclohexane, Ancamine 2167, Ancamine 2264 (manufactured by Evonik), etc. Modified products of these may also be used. Specific examples include Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sunmide IM-544, Sunmide I-544, Ancamine 2075, Ancamine 2280, Ancamine 1934, and Ancamine 2228, all manufactured by Evonik; Daitoclar F-5194 and Daitoclar B-1616, all manufactured by Daito Sangyo; Lamiron C-260, all manufactured by BASF; and Fujicure FXD-821 and Fujicure 4233, all manufactured by T&K TOKA. These may be used alone or in combination of two or more.

[0125] The amount of the amine (E1) having an alicyclic structure used is preferably 1 part by weight or more and 40 parts by weight or less, more preferably 3 parts by weight or more and 35 parts by weight or less, and even more preferably 5 parts by weight or more and 25 parts by weight or less, based on 100 parts by weight of the epoxy resin (C).

[0126] <<Amino alcohol compounds (E2)>> The amino alcohol compound (E2) used in the second embodiment is an organic compound having an amino group and an alcoholic hydroxyl group. By blending this compound, the curable composition according to the second embodiment can exhibit a relatively high rigidity by a relatively short heating step. The hydroxyl group bonded to the aromatic ring is called a phenolic hydroxyl group and is not included in the alcoholic hydroxyl group in the present application.

[0127] The amino alcohol compound (E2) is preferably an amino alcohol compound without an aromatic ring, specifically, an aliphatic compound having an amino group and an alcoholic hydroxyl group or an alicyclic compound having an amino group and an alcoholic hydroxyl group. An aliphatic compound having an amino group and an alcoholic hydroxyl group is more preferred, and an alkane compound having an amino group and an alcoholic hydroxyl group is even more preferred. Specifically, monoalcohol amines such as methanolamine, ethanolamine, propanolamine, dimethylaminoethanol, and N-methylethanolamine; dialcohol amines such as diethanolamine and dipropanolamine; and trialcohol amines such as triethanolamine and tripropanolamine. Trialcohol amines are preferred, and triethanolamine is particularly preferred.

[0128] The amount of the amino alcohol compound (E2) used is preferably 1 part by weight or more and 40 parts by weight or less, more preferably 3 parts by weight or more and 35 parts by weight or less, and even more preferably 5 parts by weight or more and 25 parts by weight or less, based on 100 parts by weight of the epoxy resin (C). The amine (E1) having an alicyclic structure and the aminoalcohol compound (E2) may be used in combination.

[0129] <<Silanol condensation catalyst (F)>> It is preferable to use a silanol condensation catalyst (F) for the purpose of promoting the condensation reaction of the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) and chain-extending or crosslinking the polymer.

[0130] Examples of the silanol condensation catalyst (F) include organotin compounds, metal carboxylates, amine compounds, carboxylic acids, and alkoxy metals.

[0131] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dioctyltin oxide with a silicate compound, and a reaction product of dibutyltin oxide with a phthalate ester.

[0132] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, etc. As the metal carboxylate, the following carboxylic acids can be combined with various metals.

[0133] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0134] 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.

[0135] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxy titanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0136] When the silanol condensation catalyst (F) is used, the amount used is preferably from 0.001 to 20 parts by weight, more preferably from 0.01 to 15 parts by weight, and even more preferably from 0.01 to 10 parts by weight, per 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0137] <<Water(G)>> Water (G) may be added to the component B of the curable composition. By adding water, the curing of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) is promoted when the components A and B are mixed.

[0138] The amount of water (G) added is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). The curable composition may contain a C agent containing water (G) in addition to the A agent and the B agent. In this case, the curable composition is a three-liquid type.

[0139] <<Other additives>> In addition to the polyoxyalkylene polymer (A), the (meth)acrylic acid ester polymer (B), the epoxy resin (C), the epoxy resin curing agent (D), the amine having an alicyclic structure (E1), the amino alcohol compound (E2), the silanol condensation catalyst (F), and the water (G), additives such as fillers, adhesion promoters, antisagging agents, antioxidants, light stabilizers, ultraviolet absorbers, tackifier resins, and other resins may be added to the curable composition. In addition, various additives may be added to the curable composition as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, plasticizers, solvents, diluents, photocurable substances, oxygen curable substances, surface improvers, silicates, curability regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, and foaming agents.

[0140] <Filling agent> Various fillers can be blended into the curable composition. Examples of fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrated silicic acid, alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament. It is more preferable to use fumed silica because it can efficiently impart thixotropy.

[0141] The amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0142] For the purpose of reducing the weight (specific gravity) of the composition, organic balloons or inorganic balloons may be added.

[0143] <Adhesion promoter> An adhesion promoter may be added to the curable composition. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added.

[0144] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltrimethoxysilane; Examples of such silanes include isocyanate group-containing silanes such as cyanate propyl methyl dimethoxy silane, α-isocyanate methyl trimethoxy silane, and α-isocyanate methyl dimethoxy methyl silane; mercapto group-containing silanes such as γ-mercapto propyl trimethoxy silane, γ-mercapto propyl triethoxy silane, and γ-mercapto propyl methyl dimethoxy silane; and epoxy group-containing silanes such as γ-glycidoxy propyl trimethoxy silane and β-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane.

[0145] The adhesion promoter may be used alone or in combination of two or more kinds. Also, reaction products of various silane coupling agents may be used.

[0146] The amount of the adhesion promoter used 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 total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0147] <Anti-sagging agent> If necessary, a sagging prevention agent may be added to the curable composition to prevent sagging and improve workability. The sagging prevention agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These sagging prevention agents may be used alone or in combination of two or more.

[0148] The amount of the sagging prevention agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0149] <Antioxidants> An antioxidant (antiaging agent) can be used in the curable composition. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

[0150] The amount of the antioxidant used 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 total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0151] <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. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.

[0152] The amount of the light stabilizer used 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 total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0153] <Ultraviolet absorbing agent> The curable composition can contain an ultraviolet absorber. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred, and examples of such compounds include those commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329 and Tinuvin 571 (all manufactured by BASF).

[0154] The amount of the ultraviolet absorber used 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 total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0155] <Tackifier resin> A tackifier resin can be added to the curable composition for the purpose of increasing the adhesiveness or adhesion to the substrate or for other reasons. There are no particular limitations on the tackifier resin, and any commonly used resin can be used.

[0156] Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.

[0157] The amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B).

[0158] <<Preparation of Curable Composition>> The curable composition according to the first embodiment is preferably prepared as a two-component composition by mixing the polyoxyalkylene polymer (A), the acrylic ester polymer (B), the epoxy resin curing agent (D), the amine (E1) having an alicyclic structure, and other additives as agent A, and the epoxy resin (C) and other additives as agent B, and mixing the agents A and B before use. In order to promote the curing reaction of the polyoxyalkylene polymer (A) and the acrylic ester polymer (B), a silanol condensation catalyst (F) and / or water (G) may be added to the agent B.

[0159] The curable composition according to the second embodiment is preferably prepared as a two-component composition by mixing the polyoxyalkylene polymer (A), the acrylic acid ester polymer (B), the epoxy resin curing agent (D), and other additives as the component A, and the epoxy resin (C) and other additives as the component B, and mixing the components A and B before use. The amino alcohol compound (E2) may be mixed in either or both of the components A and B. In addition, in order to promote the curing reaction of the polyoxyalkylene polymer (A) and the acrylic acid ester polymer (B), a silanol condensation catalyst (F) and / or water (G) may be added to the component B.

[0160] The curable composition according to the present embodiment may be cured at room temperature or may be cured by heating. When bonding different materials with an adhesive, especially when curing by heating, thermal distortion due to the difference in the linear expansion coefficient of the different materials may become a problem. Usually, when a reaction-curing adhesive such as an epoxy-based composition or a urethane-based composition having high rigidity is cured by heating, high adhesive strength is obtained, and flexibility is greatly reduced, and thermal distortion may occur when cooling. On the other hand, the curable composition according to the present embodiment is rubber-like with a Young's modulus of several MPa to several tens of MPa even when it is cured by heating to a degree that high adhesive strength is obtained, and the occurrence of thermal distortion can be suppressed. Furthermore, since high rigidity can be expressed by subsequent room temperature curing, it is possible to produce a high-rigidity adhesive that does not generate thermal distortion.

[0161] From the viewpoint of achieving both high rigidity and flexibility, the cured product obtained by curing the curable composition according to this embodiment preferably has a Young's modulus of 90 MPa or more, and more preferably 200 MPa or more, at 23° C. In addition, the elongation at break at 23° C. is preferably 70% or more, and more preferably 80% or more. The Young's modulus and the elongation at break are measured according to the method described in the Examples section.

[0162] <<Surface treatment of substrate>> The curable composition according to the present embodiment can exhibit good adhesion to various adherends such as plastics, metals, and composites. In addition, when used as an adhesive for non-polar materials such as polypropylene and engineering plastics having rigid molecular chains such as polyphenylene sulfide, the adherend can be surface-treated in advance by a known method in order to increase adhesion to these adherends and obtain stable adhesive strength. For example, surface treatment techniques such as sanding, frame treatment, corona discharge, arc discharge, and plasma treatment can be used. Plasma treatment is preferred because it causes less damage to the adherend and obtains stable adhesion. These surface treatments are also effective for removing the release agent that is used during molding and remains on the adherend surface.

[0163] The curable composition according to the present embodiment has the characteristic that it exhibits the desired physical properties by performing a long-term curing (aging) process after bonding the adherends, while the stiffness rises quickly. That is, when the semi-cured product is obtained by subjecting the curable composition before curing to a relatively short heating process after bonding the adherends, the semi-cured product can exhibit a certain degree of stiffness, although it does not reach the final stiffness. For this reason, the curable composition according to the present embodiment can be suitably used as a structural adhesive for bonding adherends in a continuous line production system.

[0164] The conditions for the above-mentioned short-time heating step are not particularly limited, but examples include a temperature of 50 to 200° C. and a time of 1 minute to 1 hour.

[0165] In addition, the conditions for the final curing (curing) step carried out after the short-time heating step for the curable composition to exhibit the final desired physical properties are not particularly limited. Examples of the conditions include a temperature of 5 to 50°C and a time of 24 hours to 1 week.

[0166] <<Applications>> The curable composition is suitable for use as an adhesive composition, and can be used as a sealing material, adhesive, pressure sensitive adhesive, waterproofing material, etc. for buildings, ships, automobiles, roads, etc. The cured product obtained by curing the curable composition has high rigidity but also flexibility, and is more preferably used as an adhesive, especially a structural adhesive, among the above-mentioned applications. In particular, when joining dissimilar materials such as aluminum-steel and aluminum-composite materials, the linear expansion coefficients of the two materials are different, so that thermal distortion occurs due to temperature changes. In such cases, an adhesive with high elongation is preferable to accommodate thermal deformation, so the curable composition can be suitably used for joining the dissimilar materials. In joining dissimilar materials, it is preferable to cover the joint with a sealer to prevent corrosion. As the sealer, it is possible to use a polymer having a reactive silicon group as shown in the present application. The curable composition is preferably used as an adhesive for automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical parts, various machine parts, etc. EXAMPLES

[0167] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0168] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8120GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0169] The terminal-converted molecular weight in the examples is a molecular weight calculated by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0170] The average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer (Q) shown in the Examples was calculated by the following formula. (Average number of introductions) = [unsaturated group concentration (mol / g) of polymer (Q) calculated from iodine value - unsaturated group concentration (mol / g) of precursor polymer (P) calculated from iodine value] / [hydroxyl group concentration (mol / g) of precursor polymer (P) calculated from hydroxyl value].

[0171] The average number of silyl groups introduced per terminal of the polymer (A) shown in the examples was calculated by NMR measurement.

[0172] (Synthesis Example 1) Polyoxypropylene glycol with a number average molecular weight of about 2,000 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) with a number average molecular weight of 28,500 (terminal group equivalent molecular weight 17,700) and molecular weight distribution Mw / Mn=1.21 having hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After distilling off the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene and reacted at 130°C for 2 hours. Then, 0.28 molar equivalent of sodium methoxide in methanol was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene were mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the water was removed by centrifugation. The obtained hexane solution was further mixed and stirred with 300 parts by weight of water, and the water was removed again by centrifugation, and the hexane was removed by volatilization under reduced pressure. As a result, polyoxypropylene (Q-1) having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that polymer (Q-1) had an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

[0173] 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the polyoxypropylene (Q-1) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal, and 2.2 parts by weight of trimethoxysilane was slowly dropped while stirring. The mixed solution was reacted at 90°C for 2 hours, and then the unreacted trimethoxysilane was distilled off under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (A-1) having an average of 1.6 trimethoxysilyl groups at one terminal, an average of 3.2 silicon groups per molecule, and a number average molecular weight of 28,500.

[0174] (Synthesis Example 2) 48.6 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 22.7 parts by weight of isobutanol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutanol solution (solid content 60%) of reactive silicon group-containing (meth)acrylic acid ester polymer (B-1) having an average of 1.6 silicon groups per molecule and a number average molecular weight of 2,300. The reactive silicon group equivalent of the solid content is 0.72 mmol / g.

[0175] (Synthesis Example 3) 0.42 parts by weight of cuprous bromide and 20.0 parts by weight of butyl acrylate were added to a deoxygenated reactor and heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent and 1.90 parts by weight of ethyl 2-bromoadipate as an initiator were added and mixed, and the temperature of the mixed liquid was adjusted to about 80°C, at which point pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to start the polymerization reaction. Next, 80.0 parts by weight of butyl acrylate were gradually added to advance 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 by degassing under reduced pressure to obtain a polymer concentrate. The concentrate was diluted with toluene, and a filter aid, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Chemical Industry), and hydrotalcite (Kyoward 500SH: manufactured by Kyowa Chemical Industry) were added, and the mixture was heated and stirred at about 80 to 100° C., after which the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude polymer. The crude polymer, 1.98 parts by weight of potassium acrylate, 100 ppm of 4-hydroxy-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent were added and reacted at 70°C for 3 hours, after which the solvent was distilled off under reduced pressure to obtain a polymer concentrate. The concentrate was diluted with toluene, and the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a macromonomer (b2-1) having an acryloyl group at one end, a number average molecular weight of 10,500 (GPC molecular weight), and a molecular weight distribution (Mw / Mn) of 1.18.

[0176] (Synthesis Example 4) 48.0 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 60.0 parts by weight of methyl methacrylate, 10.0 parts by weight of stearyl methacrylate, 20 parts by weight of the macromonomer (b2-1) prepared in Synthesis Example 2, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 22.7 parts by weight of isobutanol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutanol solution (solid content 60%) of a reactive silicon group-containing (meth)acrylic acid ester polymer (B-2) having a number average molecular weight of 2,120 (GPC molecular weight). The solid content of the solution had a macromonomer equivalent of 0.018 mmol / g and a reactive silicon group equivalent of 0.72 mmol / g.

[0177] Example 1 42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the (meth)acrylic acid ester polymer (B-1) obtained in Synthesis Example 2 were mixed so that the solid content was 28 parts by weight, and then the isobutanol was heated and removed. The mixture obtained was mixed with 4 parts by weight of Ancamine K54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Evonik) as an epoxy resin curing agent (D), 3 parts by weight of isophoronediamine (also known as 3-(aminomethyl)-3,5,5-trimethylcyclohexaneamine) as an amine having an alicyclic structure (E1), and 2 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent to obtain Agent A. Agent B was prepared by mixing 30 parts by weight of jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), 0.3 parts by weight of Neostan U-810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) as the silanol condensation catalyst (F), and 0.5 parts by weight of water.

[0178] (Dumbbell Tensile Properties) A sheet with a thickness of about 2 mm was prepared by mixing the A and B components, and a heating process was performed at 80°C for 30 minutes. The sheet was punched into a No. 3 dumbbell shape and a tensile strength test was performed at 23°C and 50% RH to measure the stress at 30% elongation (M30), strength at break (TB), elongation at break (EB), and Young's modulus. Tensile properties other than Young's modulus were measured at a tensile speed of 200 mm / min using an autograph (AGS-J) made by Shimadzu Corporation. Young's modulus was measured at a tensile speed of 10 mm / min, with a displacement range of 0.05 to 0.3%. The results are shown in Table 1.

[0179] (Examples 2-3 and Comparative Examples 1-4) A composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the dumbbell tensile properties were evaluated. The results are shown in Table 1.

[0180] In addition, the following compounds were used in Table 1. (1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik) (2): 4,4'-diaminodicyclohexylmethane (3): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) (4): Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation) (5): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

[0181] [Table 1]

[0182] As shown in Table 1, in Example 1-3 in which the amine (E1) having an alicyclic structure was blended, the rigidity (Young's modulus) exhibited by a short heating step of 80°C for 30 minutes was higher than that of Comparative Example 1 in which the amine (E1) having an alicyclic structure was not blended. This shows that the incorporation of the amine (E1) having an alicyclic structure improved the rigidity exhibited by the heating step.

[0183] It is also evident that Examples 1 and 2, which used an amine compound in which an amino group is directly bonded to an alicyclic skeleton, exhibit higher rigidity through the heating step than Example 3, which used an amine compound in which an amino group is not directly bonded to an alicyclic skeleton.

[0184] On the other hand, the rigidity shown in Comparative Example 2-4, in which an amine compound having no alicyclic structure was blended, was about the same as that of Comparative Example 1. This shows that the rigidity improving effect is specific to the amine (E1) having an alicyclic structure.

[0185] In addition, for Example 1, as described above, the A and B agents were mixed to prepare a sheet with a thickness of about 2 mm, and the sheet was heated at 80°C for 30 minutes, and then cured at 23°C for 7 days. Thereafter, the sheet was punched into a No. 3 dumbbell shape as described above, and a tensile strength test was performed. The measured M30 was 10.5 MPa, TB was 14.0 MPa, Young's modulus was 270 MPa, and EB was 230%. From this, it can be seen that the curable composition of Example 1 exhibits good cured product properties that can be used as a structural adhesive after being cured for a sufficient period of time.

[0186] Example 4 42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the (meth)acrylic acid ester polymer (B-2) obtained in Synthesis Example 4 were mixed so that the solid content was 28 parts by weight, and then the isobutanol was heated to remove the volatiles. The obtained mixture was mixed with 7 parts by weight of Ancamine K54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Evonik) as an epoxy resin curing agent (D), 4 parts by weight of Amicure PACM (4,4'-diaminodicyclohexylmethane, manufactured by Evonik) as an amine having an alicyclic structure (E1), 7 parts by weight of p-dodecylphenol as a phenolic compound, 2 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and 2 parts by weight of AEROSIL R-202 (hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.) and 4.5 parts by weight of AEROSIL 300 (hydrophilic fumed silica, manufactured by Nippon Aerosil Co., Ltd.) as fillers to obtain Agent A. Agent B was prepared by mixing 31.7 parts by weight of jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), 4 parts by weight of Silohorbic 200 (hydrophobic colloidal silica, manufactured by Fuji Silysia Chemical Co., Ltd.) and 1.5 parts by weight of AEROSIL R-202 (hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.) as the filler, 0.3 parts by weight of Neostan U-810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) as the silanol condensation catalyst (F), and 0.5 parts by weight of water. The dumbbell tensile properties were evaluated in the same manner as in Example 1. However, the curing conditions were changed to heating at 80° C. for 15 minutes, followed by curing at 23° C. and a relative humidity of 50% for 7 days. The results are shown in Table 2.

[0187] Example 5 A composition was prepared in the same manner as in Example 4 except that the formulation was changed as shown in Table 2, and the dumbbell tensile properties were evaluated. The results are shown in Table 2.

[0188] In addition, the following compounds were used in Table 2. (1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik) (2): 4,4'-diaminodicyclohexylmethane (3): 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (4): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) (5): Hydrophobic fumed silica (Nippon Aerosil Co., Ltd.) (6): Hydrophilic fumed silica (Nippon Aerosil Co., Ltd.) (7): Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation) (8): Hydrophobic colloidal silica (Fuji Silysia Chemical Co., Ltd.) (9): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

[0189] [Table 2]

[0190] As shown in Table 2, in Examples 4 and 5, a compound in which an amino group is directly bonded to an alicyclic skeleton was used as the amine (E1) having an alicyclic structure, and curing was carried out for a sufficient period of time to obtain a cured product with high rigidity (Young's modulus).

[0191] Example 6 42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the (meth)acrylic acid ester polymer (B-1) obtained in Synthesis Example 2 were mixed so that the solid content was 28 parts by weight, and then the isobutanol was heated and removed. The mixture obtained was mixed with 4 parts by weight of Ancamine K54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Evonik) as an epoxy resin curing agent (D), 3 parts by weight of triethanolamine as an amino alcohol compound (E2), and 2 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent to obtain Agent A. Agent B was prepared by mixing 30 parts by weight of jER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), 0.3 parts by weight of Neostan U-810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) as the silanol condensation catalyst (F), and 0.5 parts by weight of water. The dumbbell tensile properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0192] (Example 7 and Comparative Examples 5-6) A composition was prepared in the same manner as in Example 6 except that the formulation was changed to that shown in Table 3, and the dumbbell tensile properties were evaluated. The results are shown in Table 3.

[0193] In addition, the following compounds were used in Table 3. (1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik) (2): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) (3): Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation) (4): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

[0194] [Table 3]

[0195] As shown in Table 3, in Examples 6 and 7 in which the amino alcohol compound (E2) was blended, the rigidity (Young's modulus) exhibited by a short heating step of 80°C for 30 minutes was higher than that of Comparative Example 5 in which the amino alcohol compound (E2) was not blended, or Comparative Example 6 in which the epoxy resin (C) was not blended. Also, it was found that Example 6 in which triethanolamine, a trialcoholamine, was blended, had a higher rigidity than Example 7 in which 2-dimethylaminoethanol, a monoalcoholamine, was blended.

[0196] In addition, for Example 6, as described above, the A and B agents were mixed to prepare a sheet with a thickness of about 2 mm, and the sheet was heated at 80°C for 30 minutes, and then cured at 23°C for 7 days. After that, the sheet was punched into a No. 3 dumbbell shape as described above, and a tensile strength test was performed. The measured M30 was 6.0 MPa, TB was 9.2 MPa, Young's modulus was 90 MPa, and EB was 180%. From this, it can be seen that the curable composition of Example 6, after being cured for a sufficient period of time, exhibits good cured product properties that can be used as a structural adhesive.

Claims

1. an agent A including a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by general formula (1), an epoxy resin curing agent (D) having a tertiary amine other than an amine having an alicyclic structure, and an amine (E1) having an alicyclic structure; Agent B containing an epoxy resin (C); A multi-component curable composition comprising: -SiR ５ ｃ X ３－ｃ (1) (In the formula, R ５ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1.

2. The multi-component curable composition according to claim 1 , wherein the amine (E1) having an alicyclic structure is a compound in which an amino group is directly bonded to an alicyclic skeleton.

3. an agent A including a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1), a (meth)acrylic acid ester polymer (B) having a reactive silicon group represented by general formula (1), and an epoxy resin curing agent (D) having a tertiary amine other than an aminoalcohol compound; Agent B containing an epoxy resin (C); A multi-component curable composition comprising: A multi-component curable composition, in which either or both of the components A and B contain an amino alcohol compound (E2). -SiR ５ ｃ X ３－ｃ (1) (In the formula, R ５ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c is 0 or 1.

4. The multi-component curable composition according to claim 3 , wherein the amino alcohol compound (E2) is an amino alcohol compound having no aromatic ring.

5. The multi-component curable composition according to claim 3 or 4, wherein the amino alcohol compound (E2) is a trialcoholamine.

6. 6. The multi-component curable composition according to claim 1, wherein the reactive silicon group of the (meth)acrylic acid ester polymer (B) is a trimethoxysilyl group.

7. The terminal portion of the polyoxyalkylene polymer (A) is represented by the general formula (2): 【Chemistry 1】 (In the formula, R １ , R ３ are each independently a divalent linking group having 1 to 6 carbon atoms, R １ , R ３ The atoms in R 1 and R 3 that are bonded to the carbon atoms adjacent to R are carbon, oxygen, or nitrogen. ２ , R ４ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 10. R ５ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X is a hydroxyl group or a hydrolyzable group; and c is 0 or 1. The multi-component curable composition according to any one of claims 1 to 6,

8. R １ CH ２ OCH ２ and R ３ CH ２ The multi-component curable composition according to claim 7,

9. R ２ and R ４ The multi-component curable composition according to claim 7 or 8, wherein each of the is a hydrogen atom.

10. The multi-component curable composition according to any one of claims 1 to 9, wherein the reactive silicon group of the polyoxyalkylene polymer (A) is a trimethoxysilyl group.

11. The multi-component curable composition according to any one of claims 1 to 10, wherein the (meth)acrylic acid ester polymer (B) is a polymer having, as constituent monomers, a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer (b2) which is a (meth)acrylic acid ester polymer having a polymerizable unsaturated group.

12. A structural adhesive comprising the multi-component curable composition according to any one of claims 1 to 11.

13. A cured product obtained by curing the multi-component curable composition according to any one of claims 1 to 12.

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