Curable composition

Abstract

To provide a curable composition capable of exhibiting superior deep curing properties in the early stage of curing, even when it contains both a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylic polymer having a reactive silicon group.SOLUTION: A curable composition comprises a polyoxyalkylene-based polymer (A) having a reactive silicon group, a (meth)acrylic-based polymer (B) having a reactive silicon group, and an adhesion-imparting agent (C), wherein the adhesion-imparting agent (C) used has a surface tension of 20 to 110 mN / m as calculated at 23°C according to the parachor method.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic polymer (B) having a reactive silicon group, and an adhesion promoter (C). [Background technology]

[0002] Organic polymers having at least one reactive silicon group in the molecule can be crosslinked even at room temperature by forming siloxane bonds accompanied by hydrolysis of the silyl groups due to moisture, etc. It is known that organic polymers having reactive silicon groups have the property of giving rubber-like cured products through such crosslinking reactions.

[0003] Among organic polymers having reactive silicon groups, polyoxyalkylene polymers having reactive silicon groups and (meth)acrylic polymers having reactive silicon groups are widely used in construction sealants and industrial sealants (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-221501 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a curable composition containing a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylic polymer having a reactive silicon group is cured, there is a problem that the deep curing property is poor in the early stage of curing due to the curing caused by moisture or the like.

[0006] The present invention has been made in view of the above-mentioned problems, and aims to provide a curable composition that exhibits excellent deep curing properties in the early stage of curing, even when it contains a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylic polymer having a reactive silicon group. [Means for solving the problem]

[0007] The present inventors have discovered that the above-mentioned problems can be solved by using an adhesion promoter (C) having a surface tension of 20 to 110 mN / m, calculated as a value at 23°C according to the Parachor method, in a curable composition containing a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic polymer (B) having a reactive silicon group, and an adhesion promoter (C), and have thus completed the present invention.

[0008] More specifically, the present invention provides the following (1) to (5). (1) A composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic polymer (B) having a reactive silicon group, and an adhesion promoter (C), the (meth)acrylic polymer (B) contains a structural unit derived from a (meth)acrylic acid alkyl ester, A curable composition, wherein the surface tension of the adhesion promoter (C) is 20 to 110 mN / m, as calculated as a value at 23°C according to the Parachor method. (2) The curable composition according to (1), wherein the adhesion promoter (C) is at least one selected from the group consisting of polyethyleneimine, silicone oil having reactive groups at both ends, silane coupling agents having dicarboxylic anhydride groups, and silane coupling agents having epoxy groups. (3) The curable composition according to (1) or (2), wherein the adhesion promoter (C) comprises a silane coupling agent having a polyethyleneimine and a dicarboxylic acid anhydride group, or a silane coupling agent having a polyethyleneimine and an epoxy group. (4) The curable composition according to any one of (1) to (3), wherein the adhesion promoter (C) comprises a silicone oil having reactive groups at both ends and a silane coupling agent having a dicarboxylic acid anhydride group, or a silicone oil having reactive groups at both ends and a silane coupling agent having an epoxy group. (5) The curable composition according to any one of (2) to (4), wherein the reactive group is at least one selected from the group consisting of an amino group, a dicarboxylic acid anhydride group, an epoxy group, a reactive silicon group, a hydroxy group, a mercapto group, a carboxy group, and a (meth)acrylic group. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a curable composition that exhibits excellent deep curing properties in the early stage of curing, even when it contains a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylic polymer having a reactive silicon group. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below.

[0011] ≪Curable composition≫ The curable composition contains a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic polymer (B) having a reactive silicon group, and an adhesion promoter (C). The (meth)acrylic polymer (B) contains a structural unit derived from a (meth)acrylic acid alkyl ester. The surface tension of the adhesion promoter (C), calculated as a value at 23° C. according to the Parachor method, is 20 to 110 mN / m. The curable composition may also contain various other additives, if necessary.

[0012] Essential and optional components that the curable composition may contain are described below.

[0013] <Polyoxyalkylene polymer (A)> The polyoxyalkylene polymer (A) (hereinafter sometimes simply referred to as "polymer (A)") has a reactive silicon group at the end of the molecular chain. The reactive silicon group is not particularly limited as long as it can form a siloxane bond. Preferred examples of the reactive silicon group include those represented by the following formula (1): -SiR 1 3-a X a (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 3SiO- represents a triorganosiloxy group. 0 is a hydrocarbon group having 1 to 20 carbon atoms. 0 may be the same or different, X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 , or when there are multiple Xs, multiple R 1 , or multiple Xs may be the same or different.) Examples of reactive silicon groups include those represented by the following formula: Polymer (A) has a polymer backbone and a polymer chain end bonded to the polymer backbone. In the specification and claims of this application, the polymer backbone is also referred to as the "main chain structure." The polymer backbone is a structure in which multiple structural units derived from monomers are bonded in succession. The monomer may be one type or multiple types.

[0014] The polymer chain end is a moiety located at the end of the polymer (A). The number of polymer chain ends of the polymer (A) is 2 when the main chain structure is linear, and 3 or more when the polymer backbone is branched. When the polymer (A) is a mixture of a polymer having a linear main chain structure and a polymer having a branched main chain structure, the number of polymer chain ends is an average value between 2 and 3.

[0015] The reactive silicon group may be present in the polymer backbone or at the polymer chain terminal. Furthermore, two or more reactive silicon groups may be present at the polymer chain terminal. When the curable composition is used as an adhesive, a sealant, an elastic coating agent, a pressure-sensitive adhesive, or the like, it is preferred that the reactive silicon group in the polymer (A) be present at the polymer chain terminal.

[0016] <Reactive silicon group> The reactive silicon group is a group that can generate a silanol group by hydrolysis. When the reactive silicon group generates a silanol group, the polymer (A) is crosslinked by a condensation reaction between the silanol groups. As mentioned above, the reactive silicon group is not particularly limited, but the reactive silicon group is preferably a group represented by the following formula (1): -SiR 1 3-a X a (1)

[0017] In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 3SiO- represents a triorganosiloxy group. 0 is a hydrocarbon group having 1 to 20 carbon atoms. 0 may be the same or different. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 , or when there are multiple Xs, multiple R 1 Alternatively, multiple Xs may be the same or different.

[0018] R in formula (1) 1Specific examples of R include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; alkoxymethyl groups such as methoxymethyl; halogenated methyl groups such as chloromethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, toluyl, and 1-naphthyl; and aralkyl groups such as benzyl. Among these groups, alkyl and aryl groups are preferred, with methyl, ethyl, and phenyl groups being more preferred, methyl and ethyl groups being even more preferred, and methyl being particularly preferred. In formula (1), R 1 If there are multiple R 1 may be the same group or a combination of two or more different groups.

[0019] X in formula (1) is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be a known hydrolyzable group. Specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, 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, and an alkenyloxy group. Among these, an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferred, and an alkoxy group such as a methoxy group and an ethoxy group is more preferred because of its mild hydrolysis and ease of handling. A methoxy group is preferred because it allows for easy adjustment of the curability of the curable composition.

[0020] The reactive silicon group represented by formula (1) is not particularly limited. Specific examples of the reactive silicon group represented by formula (1) include dimethoxymethylsilyl, diethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, dimethoxyphenylsilyl, methoxymethyldimethoxysilyl, methoxymethyldiethoxysilyl, triisopropenyloxysilyl, and triacetoxysilyl. Among these, dimethoxymethylsilyl and trimethoxysilyl are preferred because they facilitate the synthesis of polymer (A). Trimethoxysilyl and methoxymethyldimethoxysilyl are preferred because they have excellent curability. Dimethoxymethylsilyl is particularly preferred because it has excellent stability.

[0021] (Main chain structure of polymer (A)) The polymer (A) is a polyoxyalkylene polymer. Therefore, the main chain structure of the polymer is made of a polyoxyalkylene polymer. Specific examples of the main chain structure of the polymer (A) include polyoxyalkylene polymers such as polyoxyethylene polymers, polyoxypropylene polymers, polyoxybutylene polymers, polyoxytetramethylene polymers, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers.

[0022] Among polyoxyalkylene polymers, polyoxypropylene is preferred as the main chain structure because it has excellent deep curing properties as a one-component composition due to its high moisture permeability and also has excellent adhesive properties.

[0023] The polyoxyalkylene polymer is -R 3 It is a polymer having a repeating unit represented by -O-. 3 R is a linear or branched alkylene group having 1 to 14 carbon atoms. 3 As —R, a linear or branched alkylene group having 2 to 4 carbon atoms is more preferred. 3Specific examples of the repeating unit represented by -O- include -CHO-, -CHCHO-, -CHCH(CH)O-, -CHCH(CH)O-, -CHC(CH)(CH)O-, and -CHCHCHCHO-. The main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In particular, when the curable composition is used as a sealant, adhesive, or the like, a polyoxypropylene polymer having oxypropylene repeating units in an amount of 50% by weight or more, preferably 80% by weight or more, of the polymer main chain structure is preferred as the polyoxyalkylene polymer. This is because such polyoxyalkylene polymers are amorphous and have relatively low viscosity.

[0024] The main chain structure of the polyoxyalkylene polymer may be linear or branched.

[0025] The polyoxyalkylene polymer is preferably a polymer obtained by ring-opening polymerization of a cyclic ether compound in the presence of an initiator using a polymerization catalyst.

[0026] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, tetrahydrofuran, etc. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, propylene oxide is particularly preferred because it can give an amorphous polyether polymer having a relatively low viscosity.

[0027] Specific examples of the initiator include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and polyoxyalkylene polymers such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

[0028] The method for synthesizing the polyoxyalkylene polymer is not particularly limited. Examples of methods for synthesizing polyoxyalkylene polymers include a polymerization method using an alkali catalyst such as KOH; a polymerization method using a transition metal compound-porphyrin complex catalyst, such as the complex obtained by reacting an organoaluminum compound with porphyrin, as disclosed in JP-A-61-215623; a polymerization method using a composite metal cyanide complex catalyst, as disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, and 3,427,335; a polymerization method using a catalyst made of a polyphosphazene salt, as exemplified in JP-A-10-273512; and a polymerization method using a catalyst made of a phosphazene compound, as exemplified in JP-A-11-060722. The polymerization method using a double metal cyanide complex catalyst is more preferred because it has low production costs and can produce a polymer with a narrow molecular weight distribution.

[0029] The main chain structure of the polymer (A) may be a main chain structure of a polyoxyalkylene polymer containing bonds other than ether bonds, such as urethane bonds and urea bonds, within the range that does not significantly impair the desired effects. Specific examples of polymers having such a main chain structure include polyurethane prepolymers and polyurea prepolymers.

[0030] The polyurethane prepolymer can be obtained by a known method such as a method of reacting a polyol compound with a polyisocyanate compound, and the polyurea prepolymer can be obtained by a known method such as a method of reacting a polyamine compound with a polyisocyanate compound. The main chain structure of the polymer (A) may be the main chain structure of a prepolymer having a combination of urethane bonds and urea bonds, which is obtained by reacting a polyol compound and a polyamine compound with a polyisocyanate compound.

[0031] Specific examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol.

[0032] Specific examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.

[0033] The polyurethane prepolymer may have a terminal group of either a hydroxyl group or an isocyanate group, and the polyurea prepolymer may have a terminal group of either an amino group or an isocyanate group.

[0034] In a cured product of a curable composition containing, as the polymer (A), a polymer having one or more bonds selected from a urethane bond, a urea bond, and an ester bond in the main chain structure, the strength of the cured product may decrease due to cleavage of the urethane bond, urea bond, or ester bond in the main chain structure due to heat or the like.

[0035] When a polymer containing an amide bond in the main chain structure is used as the organic polymer, the curability of the curable composition may be improved. 4 It is represented by -C(=O)-. 4is a hydrogen atom or an organic group which may have a substituent. When the amount of amide bonds in the main chain structure is within an appropriate range, the viscosity of the polymer is low, and a decrease in strength of the cured product due to cleavage of the amide bonds due to heat or the like and an increase in viscosity of the curable composition due to storage are unlikely to occur, and the workability of the curable composition is good.

[0036] When the polymer (A) contains an amide bond in its main chain structure, the average number of amide bonds per molecule is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 3. When the average number of amide bonds per molecule is within this range, the curable composition has good curability, the viscosity of the polymer (A) is low, and the polymer (A) and the curable composition are easy to handle.

[0037] As the polymer (A) described above, a polyoxyalkylene polymer that does not contain a urethane bond, a urea bond, an ester bond, or an amide bond in the main chain structure is most preferred, from the viewpoint of obtaining a curable composition excellent in storage stability and workability.

[0038] The polymer (A) is preferably a polymer obtained by introducing a reactive silicon group into a polymer by any of the following methods (a) to (d). (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer into carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups are converted into HSiR 1 3-a X a A method of hydrosilylation using a hydrosilane represented by the formula R 1 , X, and a are the same as those in general formula (1). (b) OCN-W-SiR 1 3-a X a A method of reacting an isocyanate alkylsilane compound represented by the formula: W is a divalent organic group. 1 , X, and a are the same as those in general formula (1). (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups and HS-W-SiR1 3-a X a A method of carrying out an ene-thiol reaction with a mercaptoalkylsilane compound represented by the formula: W is a divalent organic group. 1 , X, and a are the same as those in general formula (1). (d) A hydroxyl-terminated organic polymer is reacted with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, and then the terminal NCO groups are converted into an NCO-terminated organic polymer by the reaction of HNR 5 -W-SiR 1 3-a X a , or HS-W-SiR 1 3-a X a A method of reacting a silane compound represented by the formula: W is a divalent organic group. 5 is a hydrogen atom or an alkyl group. 1 , X, and a are the same as those in general formula (1).

[0039] In the above methods (a) and (c), examples of the terminal carbon-carbon unsaturated group include a vinyl group, an allyl group, a methallyl group, an allenyl group, and a propargyl group.

[0040] In any of the above methods (b) to (d), the polymer (A) obtained by using a silane compound in which W is methylene exhibits very high curability.

[0041] Method (a) is preferred because it is easy to obtain a polymer (A) having good storage stability, while methods (b), (c), and (d) are preferred because they can achieve a high conversion rate in a relatively short reaction time.

[0042] The method for introducing a reactive silicon group by method (a) has been proposed in Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Laid-Open Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Pat. Nos. 3,632,557, 4,345,053, 4,366,307, and 4,960,844. Examples of such methods include the method proposed in Japanese Patent Laid-Open Nos. 61-197631, 61-215622, 61-215623, and 61-218632, in which reactive silicon groups are introduced by hydrosilylation or the like into a high-molecular-weight, narrow-molecular-weight distribution polyoxypropylene polymer having a number-average molecular weight of 6,000 or more and an Mw / Mn ratio of 1.6 or less, as well as the method proposed in Japanese Patent Laid-Open No. 3-72527. Furthermore, a method for introducing more than one reactive silicon group into a molecular terminal is proposed in Japanese Patent No. 6,096,320.

[0043] The number average molecular weight of the polymer (A) is not particularly limited. The number average molecular weight of the polymer (A), as polystyrene-equivalent molecular weight measured by GPC, is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is within the above range, the amount of reactive silicon groups introduced is appropriate, making it easy to obtain a polymer (A) that has a viscosity that is easy to handle and excellent workability, while keeping production costs within an appropriate range.

[0044] The molecular weight of polymer (A) can also be expressed as an end-group-converted molecular weight calculated by directly measuring the end-group concentration of the polymer precursor before the introduction of reactive silicon groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the polymer structure (the degree of branching determined by the polymerization initiator used).The end-group-converted molecular weight of polymer (A) can also be calculated by creating a calibration curve of the number average molecular weight determined by general GPC measurement of the polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight determined by GPC of polymer (A) into an end-group-converted molecular weight.

[0045] The molecular weight distribution (Mw / Mn) of the polymer (A) is not particularly limited. It is preferable that the molecular weight distribution of the polymer (A) is narrow. Specifically, the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0046] To obtain a good rubber-like cured product, the reactive silicon groups of the polymer (A) are preferably present at the polymer chain terminals. The number of reactive silicon groups per polymer chain terminal is preferably 0.5 or more and 3.0 or less on average, more preferably 0.6 or more and 2.5 or less, even more preferably 0.7 or more and 2.2 or less, and particularly preferably 0.8 or more and 2.0 or less. When the number of reactive silicon groups is 0.5 or more, the curability of the polymer (A) and the curable composition is good, and the cured product of the curable composition has good rubber elasticity.

[0047] The number of reactive silicon groups in one molecule is preferably 1 to 7 on average, more preferably 1 to 4, and particularly preferably 1 to 3.

[0048] Furthermore, as described in WO2013 / 180203, an organic polymer having two or more reactive silicon groups at the polymer chain terminals can also be used as the polymer (A). Such a polymer (A) exhibits high curability, and the resulting cured product can be expected to have high strength and high recovery.

[0049] Specific examples of commercially available polymer (A) products include various reactive silicon group-containing polyoxypropylene products such as Kaneka MS Polymer (registered trademark) and Kaneka Silyl (registered trademark). All of these commercially available polymers (A) are products of Kaneka Corporation. Other usable products include EXCESTAR (registered trademark) from AGC Corporation, GENIOSIL (registered trademark) from WACKER, and STP from RISUN POLYMER.

[0050] <(Meth)acrylic polymer (B)> The (meth)acrylic polymer (B) (hereinafter sometimes simply referred to as "polymer (B)") has a reactive silicon group at the end of the molecular chain. The reactive silicon group is not particularly limited as long as it can form a siloxane bond. The reactive silicon group is preferably a reactive silicon group represented by the above formula (1). The polymer (B) has a polymer backbone and a polymer chain end bonded to the polymer backbone. The polymer backbone is a structure in which multiple structural units derived from monomers are bonded in succession. The monomer may be one type or multiple types.

[0051] The polymer chain end is a moiety located at the end of the polymer (B). The number of polymer chain ends of the polymer (B) is 2 when the main chain structure is linear, and 3 or more when the polymer backbone is branched. When the polymer (B) is a mixture of a polymer having a linear main chain structure and a polymer having a branched main chain structure, the number of polymer chain ends is an average value between 2 and 3.

[0052] The reactive silicon group may be present in the polymer backbone or at the polymer chain terminal. Furthermore, two or more reactive silicon groups may be present at the polymer chain terminal. When the curable composition is used as an adhesive, a sealant, an elastic coating agent, a pressure-sensitive adhesive, or the like, it is preferred that the reactive silicon group in the polymer (B) be present at the polymer chain terminal.

[0053] The reactive silicon group in the polymer (B) may be the same as or different from the reactive silicon group in the polymer (A).

[0054] (Main chain structure of polymer (B)) The polymer (B) contains a structural unit derived from a (meth)acrylic acid alkyl ester. The polymer (B) may contain structural units derived from two or more types of (meth)acrylic acid alkyl esters. The (meth)acrylic acid alkyl ester means an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester.

[0055] Specific examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-undecyl acrylate, lauryl acrylate, n-tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, and behenyl acrylate.

[0056] Specific examples of methacrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, lauryl methacrylate, n-tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, and behenyl methacrylate.

[0057] The ratio of the weight of the structural units derived from a (meth)acrylic acid alkyl ester to the weight of the polymer (B) is preferably 50% by weight or more, and more preferably 70% by weight or more.

[0058] In terms of the compatibility of polymer (B) with polymer (A) and the like and the stability of polymer (B), the monomer for preparing polymer (B) is preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms.

[0059] The (meth)acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms is represented by the following formula (B1): CH2=CR b1 COOR b2 (B1) (In formula (B1), R b1 is a hydrogen atom or a methyl group. b2 is an alkyl group having 1 to 30 carbon atoms. It is expressed as:

[0060] In formula (B1), R b2 Examples of the alkyl group include alkyl groups having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, a 2-ethylhexyl group, a lauryl group, an n-tridecyl group, a cetyl group, and a stearyl group. R b2 The alkyl group as the group preferably has 1 to 20 carbon atoms.

[0061] The monomers for producing the polymer (B) may contain other monomers in addition to the alkyl (meth)acrylate ester. Other monomers include acrylic acid and methacrylic acid; (meth)acrylamides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; epoxy group-containing (meth)acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate; amino group-containing unsaturated compounds such as 2-(N,N-diethylamino)ethyl methacrylate and 2-aminoethyl vinyl ether; acrylonitrile and methacrylonitrile; styrenes such as styrene and α-methylstyrene; alkyl vinyl ethers; vinyl chloride; and fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

[0062] The molecular weight of the polymer (B) is not particularly limited as long as the desired effects are not impaired. The molecular weight of the (meth)acrylic copolymer (B) is preferably 500 to 100,000, more preferably 1,000 to 10,000, in terms of polystyrene equivalent number average molecular weight measured by GPC. The molecular weight distribution (Mw / Mn) of the polymer (B) is not particularly limited. It is preferable that the molecular weight distribution of the polymer (B) is narrow. Specifically, the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the polymer (B) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0063] The polymer (B) can be produced by a conventional vinyl polymerization method. Examples of the vinyl polymerization method include a solution polymerization method using a radical reaction and a bulk polymerization method. The vinyl polymerization method is not limited to these methods. The above polymerization reaction is typically carried out at 50 to 150° C. in the presence of monomers, a radical initiator, a chain transfer agent, a solvent, and the like. The polymerization reaction conditions are not limited to the above conditions.

[0064] Specific examples of the radical initiator include azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and benzoyl peroxide.

[0065] Specific examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan, and halogen-containing compounds.

[0066] As the solvent, for example, a solvent inactive to the polymerization reaction, such as an alcohol-based solvent, an ether-based solvent, a hydrocarbon-based solvent, or an ester-based solvent, can be preferably used. The solvents may be used alone or in combination of two or more.

[0067] Various methods are known for introducing reactive silicon groups into (meth)acrylic polymers. Specific examples include: I) A method of copolymerizing a compound having an ethylenically unsaturated double bond and a reactive silicon group with a (meth)acrylic acid alkyl ester represented by formula (B1); II) A method in which a compound having an ethylenically unsaturated double bond and a reactive functional group (e.g., acrylic acid) is copolymerized with a (meth)acrylic acid alkyl ester represented by formula (B1), and the reactive functional group in the copolymer is reacted with reactive silicon and a compound capable of reacting with the reactive group (e.g., a reactive silicon group-containing isocyanate compound); III) A method of polymerizing a (meth)acrylic acid alkyl ester represented by formula (B1) in the presence of a mercaptan having a reactive silicon group as a chain transfer agent; IV) A method of polymerizing a (meth)acrylic acid alkyl ester represented by formula (B1) using an azobisnitrile compound having a reactive silicon group or a disulfide compound having a reactive silicon group as an initiator; and V) A method of introducing a reactive silicon group into the molecular chain terminal of a polymer obtained by polymerizing an alkyl (meth)acrylate ester represented by formula (B1) by living radical polymerization can be mentioned. The method for introducing a reactive silicon group into a (meth)acrylic polymer is not limited to the above-mentioned method.

[0068] The compound having an ethylenically unsaturated double bond and a reactive silicon group used in the above method I) includes compounds represented by the following formula (B2): CH2=CR b5 COOR b6 -SiR 1 3-a X a (B2) (In formula (B2), R 1 , X, and a are R in formula (1). 1 , X, and a. R b5 is a hydrogen atom or a methyl group. b6 is an alkylene group having 1 to 6 carbon atoms. A compound represented by the following formula is preferred.

[0069] In formula (B2), R b6The alkylene group as is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethane-1,2-diyl group (ethylene group), and a propane-1,3-diyl group (trimethylene group), and is preferably an alkylene group having 1 to 4 carbon atoms.

[0070] Specific examples of compounds having an ethylenically unsaturated double bond and a reactive silicon group include γ-methacryloxypropylalkoxysilanes such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane; γ-acryloxypropylalkoxysilanes such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltriethoxysilane; and vinylalkoxysilanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane.

[0071] In the compound having an ethylenically unsaturated double bond and a reactive functional group used in the above method II), examples of the reactive functional group include an amino group, a hydroxyl group, and a carboxyl group. Examples of groups that can react with these reactive functional groups include an isocyanate group. Other examples include allyl groups as reactive functional groups, as described in JP-A-54-36395, JP-A-01-272654, and JP-A-02-214759, etc. Examples of groups that can react with allyl groups include silicon hydride groups (H—Si).

[0072] Examples of mercaptans containing a reactive silicon group that can be used as chain transfer agents in the above method III) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0073] Examples of the azobisnitrile compound having a reactive silicon group and the disulfide compound used in the above method IV) include the azobisnitrile compound having an alkoxysilyl group and the disulfide compound having an alkoxysilyl group described in JP-A-60-23405 and JP-A-62-70405.

[0074] The above method V) includes the method described in JP-A-09-272714.

[0075] Other methods include those described in JP-A Nos. 59-168014 and 60-228516, which use a mercaptan having a reactive silicon group in combination with a radical polymerization initiator having a reactive silicon group.

[0076] The number of reactive silicon groups contained in the polymer (B) is not particularly limited, and the average number of reactive silicon groups contained in the polymer (B) is preferably 0.1 to 2.0, more preferably 0.5 to 1.5, per molecule.

[0077] Weight W of polymer (B) B Weight W of polymer (A) A Ratio of W A / W B The ratio may be 1 / 99 to 99 / 1, 20 / 80 to 80 / 20, or 30 / 70 to 70 / 30.

[0078] It is common knowledge among those skilled in the art that the monomer composition of the polymer (B) is selected depending on the use and purpose of the curable composition. When the curable composition is used for applications requiring strength, such as adhesives, it is preferable that the glass transition temperature (Tg) of the polymer (B) is relatively high. Specifically, the Tg of the polymer (B) is preferably 0 to 200° C., more preferably 20 to 100° C. The Tg can be calculated by the following Fox formula.

[0079] Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi is the weight fraction of the monomer i component constituting the polymer, and Tgi is the glass transition temperature (K) of the homopolymer of monomer i.)

[0080] For example, polymethyl methacrylate is known as a (meth)acrylic polymer with a relatively high glass transition temperature (Tg). Therefore, in the monomers used to produce polymer (B), the higher the weight ratio of methyl methacrylate to the weight of the monomer, the higher the glass transition temperature (Tg) of polymer (B) tends to be. Conversely, the lower the weight ratio of methyl methacrylate to the weight of the monomer, the lower the glass transition temperature (Tg) of polymer (B) tends to be. When the curable composition is used as an adhesive, it is preferable that the weight ratio of methyl methacrylate to the weight of the monomers used in producing the polymer (B) is 50% or more, since this makes it easier to form a high-strength cured product. When the curable composition is used as a sealant, it is preferable that the ratio by weight of methyl methacrylate to the weight of the monomers used in producing the polymer (B) is less than 50%, since this results in a low viscosity of the curable composition and good workability.

[0081] <Adhesion promoter (C)> The curable composition contains an adhesion promoter (C). The adhesion promoter is a component that improves the curable composition and the adhesiveness of the curable composition by forming covalent bonds or hydrogen bonds with various components contained in the curable composition and with the surface of an article to which the curable composition is applied. The surface tension of the adhesion promoter (C), calculated as a value at 23° C. according to the Parachor method, is 20 to 110 mN / m. A curable composition containing such an adhesion promoter (C) exhibits excellent deep curing properties in the early stage of curing.

[0082] The adhesion promoter (C) is not particularly limited as long as it is a compound that exhibits a surface tension within the aforementioned range. The adhesion promoter is a component that is liquid at 23°C in terms of the aforementioned surface tension. Examples of the adhesion promoter (C) include silane coupling agents, silicone oils having reactive groups, polyethyleneimines, organic amines other than polyethyleneimines, nitrogen-containing aromatic heterocyclic compounds, organic carboxylic acids, dicarboxylic anhydrides, drying oils, carboxylic acid amides, and phosphate esters.

[0083] These compounds can form covalent bonds or hydrogen bonds with components contained in the curable composition or with the surfaces of various articles to which the curable composition is applied, thereby improving the adhesiveness of the curable composition and the cured product of the curable composition, and also improving the deep curability of the curable composition. For example, when a liquid is dropped onto a glass substrate, the lower the surface tension of the liquid, the easier it is to wet and spread on the glass substrate. In other words, the surface of a liquid with low surface tension is energetically stable, so the force that tries to sphericalize the liquid to minimize the surface area is less likely to act, resulting in good affinity with other materials. For this reason, an adhesion promoter having a surface tension that is not too high as described above is easily dispersed uniformly in the curable composition and also has good wettability with the surface of the article to which the curable composition is applied. For these reasons, it is believed that an adhesion promoter (C) exhibiting the above-mentioned specified surface tension improves the deep curing properties of the curable composition in the early stages of curing. The lower the surface tension, the better, but from the viewpoint of practical availability of the adhesion promoter (C), a surface tension of 20 mN / m or more is preferred.

[0084] Among the above adhesion promoters (C), silane coupling agents, silicone oils having reactive groups, and polyethyleneimines are preferred.

[0085] In the specification of the present application, "organic amine" is defined as a compound in which one, two, or three hydrogen atoms of ammonia are substituted with organic groups. Here, in the organic amine, the monovalent organic group is bonded to the nitrogen atom via a C-N single bond. Furthermore, in the organic amine, when two or three monovalent organic groups are bonded to the same nitrogen atom, the two organic groups may be bonded to form a ring. That is, nitrogen-containing aliphatic cyclic compounds such as piperidine compounds, piperazine compounds, and morpholine compounds are cyclic organic amine compounds. In the specification of the present application, the term "nitrogen-containing aromatic compound" refers to an aromatic compound containing a nitrogen atom as a ring-constituting atom, such as a pyrrole-based compound or a pyridine-based compound. The carboxylic acid amide may be a cyclic amide (lactam) such as 2-pyrrolidone, or may be an N-monosubstituted amide or an N,N-disubstituted amide. In the specification of the present application, organic amines and nitrogen-containing aromatic compounds are defined as compounds that do not fall under the category of silane coupling agents, silicone oils having reactive groups, and polyethyleneimines. For example, aminosilane coupling agents having an amino group and amine-modified silicone oils are not considered to be organic amines. Organic carboxylic acids are defined as compounds that do not fall under the category of silane coupling agents, silicone oils having reactive groups, polyethyleneimines, organic amines, or nitrogen-containing aromatic compounds. For example, modified silicone oils having carboxy groups, amino groups, and amino acid compounds having carboxy groups do not fall under the category of organic carboxylic acids. Dicarboxylic acid anhydrides are defined as compounds that do not fall under the categories of silane coupling agents, silicone oils having reactive groups, polyethyleneimines, organic amines, nitrogen-containing aromatic compounds, and organic carboxylic acids. For example, silane coupling agents having a dicarboxylic acid anhydride group do not fall under the category of dicarboxylic acid anhydrides. Carboxylic acid amides are defined as compounds that do not fall under the category of silane coupling agents, silicone oils having reactive groups, polyethyleneimines, organic amines, organic carboxylic acids, or dicarboxylic acid anhydrides. The phosphate ester is defined as a compound that does not fall under the category of a silane coupling agent, a silicone oil having a reactive group, a polyethyleneimine, an organic amine, an organic carboxylic acid, a dicarboxylic acid anhydride, or an amino carboxylic acid.

[0086] Hereinafter, preferred adhesion promoters (C) such as silane coupling agents, silicone oils having reactive groups, and polyethyleneimines will be described.

[0087] (Silane coupling agent) Silane coupling agents are compounds that have a hydrolyzable silicon group and a functional group other than the hydrolyzable silicon group in the molecule. In addition, condensates obtained by partially condensing silane coupling agents can also be used as silane coupling agents. Furthermore, derivatives obtained by modifying these can also be used as silane coupling agents.

[0088] The hydrolyzable group in the hydrolyzable silicon group contained in the silane coupling agent is not particularly limited. Examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, and mercapto groups. Among these, halogen atoms, alkoxy groups, alkenyloxy groups, and aryloxy groups are preferred due to their high activity. Chlorine atoms and alkoxy groups are preferred because they are easily introduced into the silane coupling agent. Alkoxy groups such as methoxy groups and ethoxy groups are more preferred because of their mild hydrolysis and ease of handling, with methoxy groups and ethoxy groups being particularly preferred. Furthermore, ethoxy groups and isopropenyloxy groups are preferred from the standpoint of safety, as the compounds that are eliminated by reaction are ethanol and acetone, respectively. The number of hydrolyzable groups bonded to the silicon atom in the silane coupling agent may be preferably three to ensure good adhesion. Furthermore, two may be preferable to ensure the storage stability of the curable composition.

[0089] The functional group other than the hydrolyzable silicon group that silane coupling agent has is not particularly limited.The functional group other than the hydrolyzable silicon group that silane coupling agent has can be exemplified by, for example, amino group, dicarboxylic acid anhydride group, epoxy group, isocyanate group, mercapto group, carboxy group, vinyl type unsaturated group, and halogeno group etc.In these groups, a part can be substituted with a substituent such as alkyl group, aralkyl group, and aryl group.

[0090] Specific examples of silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltriisopropoxysilane, 3-(2-(2-aminoethylamino)ethylamino)propyltrimethoxysilane, 3-(6-aminohexylamino)propyltrimethoxysilane, and 3-ethylamino-2-methylpropyltrimethoxysilane. Examples of suitable silanes include amino group-containing silanes such as silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-benzylaminopropyltrimethoxysilane, 3-(vinylbenzylamino)propyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, (2-aminoethylamino)methyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(trimethoxysilylpropyl)amine; and ketimine silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine.

[0091] A specific example of a silane coupling agent having a dicarboxylic acid anhydride group is 3-trimethoxysilylpropylsuccinic anhydride.

[0092] Specific examples of silane coupling agents having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0093] Specific examples of silane coupling agents having an isocyanate group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane.

[0094] Specific examples of silane coupling agents having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane.

[0095] Specific examples of silane coupling agents having a carboxy group include 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-2-(carboxymethylamino)ethyl-3-aminopropyltrimethoxysilane.

[0096] Specific examples of the silane coupling agent having a vinyl-type unsaturated group include vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-acryloyloxypropylmethyltriethoxysilane.

[0097] A specific example of the silane coupling agent having a halogeno group is 3-chloropropyltrimethoxysilane.

[0098] A condensate obtained by partially condensing the above-mentioned silane coupling agent can also be used as the silane coupling agent. However, the condensate that can be used as the silane coupling agent is a compound that has a hydrolyzable silicon group and a functional group other than the hydrolyzable silicon group in the molecule.

[0099] (Silicone oil with reactive groups) The main chain structure of silicone oil is made of polysiloxane. Silicone oil with reactive groups is silicone oil in which reactive groups are introduced into the side chain or main chain. Here, the reactive groups are functional groups that can react with functional groups of essential or optional components contained in the curable composition. This reaction includes not only chemical reactions that form covalent bonds, but also intermolecular interactions that form hydrogen bonds. The silicone oil having a reactive group is preferably a silicone oil having a reactive group at both ends of the main chain of the silicone oil.The reactive group of the silicone oil is preferably one or more selected from the group consisting of an amino group, a dicarboxylic anhydride group, an epoxy group, a reactive silicon group, a hydroxy group, a mercapto group, a carboxy group, and a (meth)acrylic group, and more preferably an amino group.

[0100] (Polyethyleneimine) The polyethyleneimine is not particularly limited as long as it has a surface tension of 20 to 110 mN / m measured under specified conditions. The polyethyleneimine can be appropriately selected from commercially available polyethyleneimines that are liquid at room temperature.

[0101] The adhesion promoter (C) explained above may be used alone or in combination of two or more.

[0102] The adhesion promoter (C) is preferably one or more selected from the group consisting of polyethyleneimine, silicone oil having reactive groups at both ends, silane coupling agents having dicarboxylic anhydride groups, and silane coupling agents having epoxy groups, and more preferably two or more selected from the group consisting of polyethyleneimine, silicone oil having reactive groups at both ends, silane coupling agents having dicarboxylic anhydride groups, and silane coupling agents having epoxy groups. The adhesion promoter (C) may contain polyethyleneimine and a silane coupling agent, or may contain silicone oil having reactive groups at both ends and a silane coupling agent. The adhesion promoter (C) may contain polyethyleneimine and a silane coupling agent having a dicarboxylic acid anhydride group, may contain polyethyleneimine and a silane coupling agent having an epoxy group, may contain silicone oil having reactive groups at both ends and a silane coupling agent having dicarboxylic acid anhydride groups, or may contain silicone oil having reactive groups at both ends and a silane coupling agent having an epoxy group.

[0103] The amount of the adhesion promoter (C) 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 weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0104] A specific method for measuring the surface tension of the adhesion promoter (C) will be described later in the Examples.

[0105] <Other additives> The curable composition may contain various additives in addition to the polyoxyalkylene polymer (A), the (meth)acrylic polymer (B), and the adhesion promoter (C), to the extent that the desired effects are not impaired. Note that the various additives may also be considered as the adhesion promoter (C). When an additive also falls under the category of the adhesion promoter (C), its amount used is included in the amount of the adhesion promoter (C) used. Examples of additives include curing catalysts, fillers, adhesion promoters, plasticizers, solvents, diluents, thixotropy-imparting agents, antioxidants, light stabilizers, ultraviolet absorbers, physical property adjusters, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, epoxy resins, other resins, surface property improvers, foaming agents, curability adjusters, flame retardants, silicates, radical inhibitors, metal deactivators, phosphorus-based peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0106] (curing catalyst) The curable composition may contain a silanol condensation catalyst as a curing catalyst for the purpose of promoting a hydrolysis condensation reaction between the reactive silicon groups of the polymer (A) and the polymer (B) and chain-extending or crosslinking the polymer. Examples of silanol condensation catalysts include organotin compounds, metal carboxylates, nitrogen-containing basic compounds, carboxylic acids, and alkoxy metals.

[0107] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin diacetylacetonate, dioctyltin diacetylacetonate, 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.

[0108] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, etc. Furthermore, as the metal carboxylate, salts of the following carboxylic acids combined with various metals can be used.

[0109] Specific examples of the nitrogen-containing basic 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.

[0110] 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.

[0111] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate). Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators. Two or more different silanol condensation catalysts may be used in combination. The amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0112] (filler) The curable composition may contain various fillers, such as reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc oxide, and resin powder; and fibrous fillers such as asbestos, glass fiber, and filament. Examples of resin powder include PVC powder and PMMA powder. When a filler is used, the amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0113] When it is desired to obtain a cured product having high strength by using these fillers, fillers selected from the group consisting of fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide are preferably used. The amount of these fillers used, which is preferable in terms of the strength of the cured product, is preferably 1 to 200 parts by weight per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). Furthermore, when a cured product with low strength and high elongation at break is desired, fillers selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasuballoon, and the like can be preferably used. The amount of these fillers used, which is preferable in terms of the elongation at break of the cured product, is preferably 5 to 200 parts by weight per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0114] Generally, the larger the specific surface area of ​​calcium carbonate, the greater the effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product. These fillers can be used alone or in combination with two or more types. Fatty acid surface-treated colloidal calcium carbonate can be used in combination with calcium carbonate with a particle size of 1 μm or more, such as untreated ground calcium carbonate.

[0115] The curable composition may contain spherical hollow bodies such as balloons for the purpose of reducing the weight (specific gravity) of the cured product. Balloons are hollow spherical fillers. Examples of balloon materials include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, saran, and acrylonitrile. The balloon material is not limited to these materials. The balloon material may also be a composite material composed of an inorganic material and an organic material. The balloon material may also be a laminate of multiple layers. One type of balloon may be used alone, or two or more types may be used in combination. The surface of the balloon may be surface-treated, coated, or treated with various surface treatment agents. For example, organic balloons coated with calcium carbonate, talc, titanium oxide, etc., or inorganic balloons surface-treated with a silane coupling agent may be used.

[0116] The particle size of the balloons is preferably 3 μm to 200 μm, and particularly preferably 10 μm to 110 μm. When the particle size of the balloons is within this range, the use of an appropriate amount of balloons can reduce the weight of the cured product to a desired extent, and a cured product can be formed while suppressing the occurrence of surface irregularities and a decrease in elongation.

[0117] When balloons are used, an anti-slip agent such as that described in JP-A-2000-154368 or an amine compound for imparting a matte finish to the surface of the cured product by providing a roughened surface such as that described in JP-A-2001-164237 can be added to the curable composition. As the amine compound, primary and / or secondary amines with a melting point of 35° C. or higher are particularly preferred.

[0118] Specific examples of balloons are described in JP-A Nos. 2-129262, 4-8788, 4-173867, 5-1225, 7-113073, 9-53063, 10-251618, 2000-154368, 2001-164237, WO97 / 05201, and the like.

[0119] The amount of spherical hollow bodies (balloons) used is preferably 0.01 to 30 parts by weight per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B). The lower limit is more preferably 0.1 part by weight, and the upper limit is more preferably 20 parts by weight. When the amount of spherical hollow bodies is within the above range, the curable composition has good properties and a cured product having excellent elongation and breaking strength is easily formed.

[0120] (Other adhesion promoters) The curable composition may contain an adhesion promoter other than the adhesion promoter (C). Examples of the adhesion promoter include a silane coupling agent having a surface tension, measured by the above-mentioned predetermined method, of less than 20 mN / m or more than 110 mN / m. A silane coupling agent is a compound having a hydrolyzable silicon group and a functional group other than the hydrolyzable silicon group in the molecule. When the curable composition is applied to various adherends, such as inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, or organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, and polycarbonate, the use of a silane coupling agent exhibits a significant adhesive improvement effect under non-primer conditions or primer-treated conditions. When the curable composition is used under non-primer conditions, the effect of improving adhesion to various adherends is particularly significant. In addition to the above functions, the silane coupling agent can also function as a dehydrating agent, a physical property adjuster, a dispersibility improver for inorganic fillers, etc.

[0121] Other preferred adhesion promoters include 3-(2-aminoethylamino)propyltrimethoxysilane and vinyltrimethoxysilane.

[0122] The other adhesion promoters may be used alone or in combination of two or more. The total amount of the adhesion promoter (C) and the other adhesion promoters 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 weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0123] (plasticizer) The curable composition may contain a plasticizer. The addition of a plasticizer can adjust the viscosity and slump of the curable composition, as well as the mechanical properties such as tensile strength and elongation of the cured product.

[0124] Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; hydrogenated phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, dioctyl succinate; Examples of suitable oils include aliphatic polycarboxylic acid ester compounds such as isodecyl and tributyl acetyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; and epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate. A specific example of a terephthalic acid ester compound is EASTMAN168 (trade name, manufactured by EASTMAN CHEMICAL). A specific example of a non-phthalic acid ester compound is Hexamoll DINCH (trade name, manufactured by BASF). A specific example of an alkylsulfonic acid phenyl ester is Mesamoll (trade name, manufactured by LANXESS).

[0125] Polymeric plasticizers can also be used. The use of polymeric plasticizers allows the initial physical properties of the cured product to be maintained for a longer period of time than when low-molecular-weight plasticizers are used. Furthermore, the drying properties (paintability) of the cured product when coated with an alkyd paint are improved.

[0126] Specific examples of polymeric plasticizers include vinyl polymers, which are polymers of vinyl monomers; esters of polyalkylene glycols and polyols, such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; polyester plasticizers obtained from dibasic acids, such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether polyols (polyoxyalkylene compounds), such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, having a number-average molecular weight of 500 or more, or even 1,000 or more; derivatives of these polyether polyols in which the hydroxyl groups have been converted to ester groups, ether groups, or the like; polystyrenes, such as poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Polymeric plasticizers are not limited to these.

[0127] The polymeric plasticizer is preferably compatible with the polyoxyalkylene polymer (A) and / or the (meth)acrylic polymer (B). From this viewpoint, polyethers and vinyl polymers are preferred. When polyethers are used as plasticizers, surface curability and deep curability are improved, and curing delay after storage does not occur. Among polyethers, polypropylene glycol is more preferred. Vinyl polymers are preferred from the viewpoint of compatibility with the polyoxyalkylene polymer (A) and / or the (meth)acrylic polymer (B) and the weather resistance and heat resistance of the cured product. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. As a method for synthesizing vinyl polymers, living radical polymerization is preferred, and atom transfer radical polymerization is more preferred, since it produces polymers with narrow molecular weight distributions and low viscosity. Furthermore, the so-called SGO process, which is described in Japanese Patent Application Laid-Open No. 2001-207157 and involves continuous bulk polymerization of an acrylic acid alkyl ester monomer at high temperature and pressure, is also preferred as a method for producing a vinyl polymer.

[0128] The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, and most preferably 1,000 to 3,000. When the number average molecular weight of the polymer plasticizer is within the above range, the initial physical properties of the cured product can be maintained over a long period of time while preventing the plasticizer from leaking out from the cured product over time due to heat, rainfall, etc., and the curable composition has an appropriate viscosity and good workability. The molecular weight distribution of the polymeric plasticizer is not particularly limited, but is preferably narrow. Specifically, the molecular weight distribution is preferably less than 1.80, more preferably 1.70 or less, even more preferably 1.60 or less, still more preferably 1.50 or less, particularly preferably 1.40 or less, and most preferably 1.30 or less.

[0129] The number average molecular weight of vinyl polymers is measured by GPC. The number average molecular weight of polyether polymers is measured by end group analysis. The molecular weight distribution (Mw / Mn) is measured by GPC (polystyrene equivalent).

[0130] The polymeric plasticizer may or may not have a reactive silicon group. When the polymeric plasticizer has a reactive silicon group, it acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product. When the polymeric plasticizer has a reactive silicon group, the number of reactive silicon groups per molecule is preferably 1 or less, more preferably 0.8 or less, on average. When using a plasticizer having a reactive silicon group, particularly a polyether polymer having a reactive silicon group, its number average molecular weight must be lower than the number average molecular weight of the polyoxyalkylene polymer (A) and / or the number average molecular weight of the (meth)acrylic polymer (B).

[0131] Among the plasticizers described above, at least one selected from the group consisting of phthalate esters, hydrogenated phthalate esters, and polyoxyalkylene compounds is preferred.

[0132] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). When the amount of plasticizer used is within the above range, it is possible to obtain the desired effects of using the plasticizer sufficiently, while forming a cured product excellent in mechanical strength. The plasticizer may be used alone, or two or more types may be used in combination. A low-molecular-weight plasticizer may be used in combination with a polymeric plasticizer. These plasticizers may be blended with the polyoxyalkylene polymer (A) or the (meth)acrylic polymer (B) when producing the polyoxyalkylene polymer (A) or the (meth)acrylic polymer (B).

[0133] (solvent, diluent) The curable composition may contain a solvent or a diluent. The solvent and diluent are not particularly limited. Examples of solvents and diluents that can be used include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When using a solvent or a diluent, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher, in order to prevent air pollution when the curable composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more.

[0134] (thixotropic agent) The curable composition may contain a thixotropy-imparting agent, if necessary, to prevent sagging and improve workability. The thixotropy-imparting agent is not particularly limited. Examples of thixotropy-imparting agents include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Examples of trade names include Disparlon 6500, Disparlon 308, Disparlon 6300, Crayvallac SL, and Crayvallac SLT. These thixotropy-imparting agents may be used alone or in combination of two or more. The amount of the thixotropy-imparting agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0135] (antioxidant) The curable composition may contain an antioxidant (antiaging agent). The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds, and hindered phenol compounds are particularly preferred. Examples of antioxidants include Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), and BHT. Hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, and ADK STAB LA-68 (all manufactured by ADEKA Corporation); SANOL LS-2626, SANOL LS-1114, and SANOL LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants that can be used include SONGNOX 4120, Naugard 445, and OKABEST CLX050. Specific examples of antioxidants are also described in Japanese Patent Application Laid-Open Nos. 4-283259 and 9-194731. 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 weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0136] (light stabilizer) The curable composition may contain a light stabilizer. The use of a light stabilizer can prevent photooxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds. As the light stabilizer, hindered amine-based compounds are particularly preferred. 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 polymer (B). Specific examples of light stabilizers are described in, for example, JP-A-9-194731.

[0137] When a photocurable substance is blended into the curable composition, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine light stabilizer as the hindered amine light stabilizer in order to improve the storage stability of the curable composition, as described in JP-A-5-70531. Tertiary amine-containing hindered amine light stabilizers include TINUVIN 123, TINUVIN 144, TINUVIN 249, TINUVIN 292, TINUVIN 312, TINUVIN 622LD, TINUVIN 765, TINUVIN 770, TINUVIN 880, TINUVIN 5866, TINUVIN B97, CHIMASSORB119FL, and CHIMASSORB944LD (all manufactured by BASF); ADK STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all manufactured by ADEKA Corporation); SANOL LS-292, LS-2626, LS-765, LS-744, and LS-1114 (all manufactured by Sankyo Lifetech Co., Ltd.), SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB CS622, and SONGSORB Examples include CS944 (all manufactured by SONGWON) and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).

[0138] (ultraviolet absorber) The curable composition may 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 compounds, benzotriazole-based compounds, salicylate-based compounds, triazine-based compounds, substituted tolyl-based compounds, and metal chelate-based compounds. Among these, benzotriazole-based compounds are particularly preferred. Specific examples of benzotriazole-based compounds include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). Specific examples of triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF), and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON).Specific examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON). 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, based on 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B). It is preferable to use a phenolic antioxidant or a hindered phenolic antioxidant in combination with a hindered amine light stabilizer and a benzotriazole ultraviolet absorber. Addworks IBC760 (manufactured by Clariant) can be used as a product containing a mixture of antioxidants, light stabilizers, and UV absorbers.

[0139] (Physical property adjuster) The curable composition may optionally contain a physical property modifier to adjust the tensile properties of the cured product. The physical property modifier is not particularly limited. Examples of the physical property modifier include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and 3-glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes having functional groups such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. The use of a physical property modifier can increase the hardness of the cured product, or conversely, decrease the hardness of the cured product and increase the elongation at break. The physical property modifiers may be used alone or in combination of two or more.

[0140] In particular, compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule are particularly preferred, with compounds that form trimethylsilanol being particularly preferred. Examples of compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule include the compounds described in JP-A-5-117521. Other examples include derivatives of alkyl alcohols such as hexanol, octanol, and decanol that hydrolyze to form trialkylsilanols such as trimethylsilanol, and derivatives of polyhydric alcohols with three or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol that hydrolyze to form trialkylsilanols such as trimethylsilanol, as described in JP-A-11-241029. Examples include derivatives of oxyalkylene polymers that produce silicon compounds that produce trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in JP-A-7-258534. Furthermore, polymers having crosslinkable hydrolyzable silicon-containing groups and silicon-containing groups that can be hydrolyzed to monosilanol-containing compounds, as described in JP-A-6-279693, can also be used. The physical property adjusting agent is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0141] (tackifying resin) The curable composition may contain a tackifying resin that is solid at room temperature and has a surface tension measured by the above-mentioned predetermined method of less than 20 mN / m or more than 110 mN / m, for the purpose of improving the adhesiveness or cohesion of the cured product to a substrate, etc. The tackifying resin is not particularly limited, and tackifying resins that are commonly used in various curable compositions can be used. Specific examples of tackifying resins 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, hydrogenated styrene block copolymers, petroleum resins, hydrogenated petroleum resins, and DCPD resins. Examples of petroleum resins include C5 hydrocarbon resins, C9 hydrocarbon resins, and C5C9 hydrocarbon copolymer resins. These may be used alone or in combination. 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 weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). Using an amount of the tackifier resin within this range allows for the formation of a cured product with good adhesion and cohesion to the substrate. The curable composition has an appropriate viscosity, and the curable composition is easy to handle.

[0142] (compounds containing epoxy groups) The curable composition may contain a compound containing an epoxy group. The use of a compound having an epoxy group can improve the recovery of the cured product. Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples of compounds having an epoxy group include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The amount of the epoxy group-containing compound used is preferably 0.5 to 50 parts by weight per 100 parts by weight of the total of the weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0143] (epoxy resin) The curable composition may contain an epoxy resin. The curable composition containing an epoxy resin is preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A epoxy resins and novolac epoxy resins. The ratio of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B) to the weight of the epoxy resin is preferably in the range of 100 / 1 to 1 / 100, expressed as a weight ratio of (weight of polymer (A) and weight of polymer (B)) / (weight of epoxy resin). When the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B) and the epoxy resin are used in the above ratio, a high-strength cured product having excellent impact strength and toughness is easily formed. When an epoxy resin is used, the curable composition may contain a curing agent together with the epoxy resin. The type of curing agent is not particularly limited, and a commonly used curing agent can be used. The amount of the curing agent used is preferably 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy resin.

[0144] (light curing substance) The curable composition may contain a photocurable substance. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Various compounds such as organic monomers, oligomers, and resins are known as photocurable substances. Many compositions containing photocurable substances are also known. Representative photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azido resins. Examples of unsaturated acrylic compounds include monomers, oligomers, and mixtures thereof having one or more acrylic unsaturated groups or methacrylic unsaturated groups. The amount of the photocurable substance 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 weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B). When the amount of the photocurable substance used falls within this range, a flexible cured product that is excellent in weather resistance and inhibits the occurrence of cracks is likely to be formed.

[0145] (oxygen curing substance) The curable composition may contain an oxygen-curing substance. Examples of oxygen-curing substances include unsaturated compounds that can react with oxygen in the air. When the curable substance contains an oxygen-curing substance, the oxygen-curing substance reacts with oxygen in the air to form a cured film near the surface of the cured product. The formation of a cured film on the surface of the cured product prevents stickiness and the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curing substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, or polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, or 1,3-pentadiene. These may be used alone or in combination of two or more. The amount of oxygen-curable substance 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 weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). Using an amount of oxygen-curable substance within this range makes it easier to form a cured product whose surface is less susceptible to contamination by dirt and dust and has excellent mechanical properties such as tensile strength. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0146] <Preparation of Curable Composition> The curable composition can be prepared as a one-component composition in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. When the curing agent composition contains a curing catalyst, the curable composition can also be prepared as a two-component composition in which a curing agent containing the curing catalyst and ingredients such as water is mixed with a separately prepared composition containing a polyoxyalkylene polymer (A) and a (meth)acrylic polymer (B) before use. From the viewpoint of workability, the one-component composition is preferred. When the curable composition is a one-component type, all ingredients are premixed, and therefore, it is preferable to dehydrate and dry the ingredients containing water before use, or to dehydrate them under reduced pressure during blending and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, or 3-glycidoxypropyltrimethoxysilane. Partially condensed silane compounds such as Evonik's Dynasylan 6490 can also be used as dehydrating agents from the standpoint of safety and stability. Among the above alkoxysilane compounds, the amount of the compound corresponding to the adhesion promoter (C) used is included in the content of the adhesion promoter (C) in the curable composition. The amount of the dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, 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 weight of the polyoxyalkylene polymer (A) and the weight of the (meth)acrylic polymer (B).

[0147] The curable composition can be used as a construction sealant, industrial adhesive, waterproof coating composition, pressure-sensitive adhesive raw material, and the like. The curable composition can also be used as a sealant for buildings, ships, automobiles, roads, and the like. Furthermore, the curable composition, alone or with the aid of a primer, can adhere to a wide range of substrates, including glass, porcelain, wood, metal, and resin moldings. Therefore, the curable composition can also be used as various types of sealing and adhesive compositions. In addition to conventional adhesives, the curable composition can also be used as a contact adhesive. Furthermore, the curable composition is useful as a food packaging material, a cast rubber material, a molding material, and a paint. The cured product of the above curable composition exhibits low water absorption. Therefore, the above curable composition and its cured product are particularly suitable for waterproof materials, such as sealants, waterproof adhesives, and waterproof coatings.

[0148] <Method of manufacturing the cured product> Before curing, the curable composition is formed into a desired shape by a method such as coating, casting, or filling.

[0149] The curable composition that has been applied, cast, or filled and shaped is cured under a desired environment, such as room temperature and humidity.

[0150] The cured product thus formed exhibits good adhesion to a variety of adherends, and in particular, exhibits excellent adhesion to materials commonly used as building materials, such as rigid polyvinyl chloride resin, mortar, and concrete. [Example]

[0151] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0152] (Synthesis Example 1) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) with a number-average molecular weight of 27,900 (17,700 molecular weight calculated as the terminal group) and a molecular weight distribution (Mw / Mn) of 1.21, bearing hydroxyl groups at both ends. Subsequently, 1.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (P-1) as a 28% methanol solution. After removing the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was then removed by vacuum devolatilization. The resulting crude polyoxypropylene was mixed with n-hexane and water, stirred, and the water was removed by centrifugation. The resulting hexane solution was then devolatilized under reduced pressure to remove metal salts from the polymer. This resulted in the production of polyoxypropylene (Q-1) having allyl groups at its termini. 500 g of this polymer (Q-1) was mixed with 50 μL of a platinum divinyldisiloxane complex solution (a 3 wt. % platinum equivalent isopropanol solution), and 4.8 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which the unreacted dimethoxymethylsilane was distilled off under reduced pressure to produce polyoxypropylene polymer (A-1) having dimethoxymethylsilyl groups at its termini and a number-average molecular weight of approximately 28,500. Polymer (A-1) contained an average of 0.8 dimethoxymethylsilyl groups at each terminus, with an average of 1.6 per molecule.

[0153] (Synthesis Example 2) A mixture of 43 g of methyl methacrylate, 204 g of butyl acrylate, 45 g of stearyl methacrylate, 7.2 g of γ-methacryloxypropyldimethoxymethylsilane, and 13 g of IBA was added dropwise to 180 g of isobutyl alcohol (IBA) heated to 105°C over 5 hours. A solution of 1.4 g of azobis-2-methylbutyronitrile as a polymerization initiator was then added dropwise to 4.5 g of IBA over 1 hour. Polymerization was then carried out after 2 hours, yielding a (meth)acrylic acid ester copolymer (B-1) with a solids concentration of 60%, a number-average molecular weight of 17,800, and an average of 1.83 dimethoxymethylsilyl groups per molecule.

[0154] (Synthesis Example 3) The (meth)acrylic acid ester copolymer (B-1) obtained in Synthesis Example 2 was mixed with 70 parts by weight of the polyoxypropylene (A-1) having dimethoxymethylsilyl groups obtained in Synthesis Example 1 so that the solid content of the (meth)acrylic acid ester copolymer was 30 parts by weight. After uniform mixing, the IBA was distilled off using a rotary evaporator to obtain an organic polymer (AB-1).

[0155] Example 1 100 parts by weight of the polymer (AB-1) obtained in Synthesis Example 3, 2 parts by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin® SP-006), 1.75 parts by weight of 3-trimethoxysilylpropylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-967C), 3 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Performance Materials Japan, LLC, trade name: SILQUEST A-171 SILAN), and 1.25 parts by weight of 3-(2-aminoethylamino)propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603) were mixed. After mixing, the resulting mixture was mixed with 2 parts by weight of dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U220H) to obtain a curable composition.

[0156] (surface tension) The surface tensions of polyethyleneimine (SP-006), 3-trimethoxysilylpropylsuccinic anhydride, and 3-(2-aminoethylamino)propyltrimethoxysilane at 23°C were calculated according to the Parachor method. The surface tension of polyethyleneimine (SP-006) was 49.3 mN / m. The surface tension of 3-trimethoxysilylpropylsuccinic anhydride was 102.4 mN / m. The surface tension of 3-(2-aminoethylamino)propyltrimethoxysilane was 62.3 mN / m.

[0157] (deep hardening) The resulting curable composition was filled into a 12 mm diameter polyethylene cylindrical container, taking care to avoid air bubbles, and the surface was smoothed to prepare a test specimen. The test specimen was cured for 16 hours at 23°C and 50% relative humidity. After curing, the cured portion of the test specimen was removed, and any uncured portion adhering to the cured portion was removed. The thickness of the cured portion was then measured using a vernier caliper. The results are shown in Table 1.

[0158] (Mortar adhesion) The resulting curable composition was applied to a mortar board measuring 25 mm x 12.5 mm and 0.5 mm thick to obtain test specimens. The test specimens were cured at 50°C and 50% relative humidity for two or four weeks. After curing, the test specimens were visually inspected for damage using the hand peel method (180° peel), and the damage was evaluated according to the following criteria. The results are shown in Table 1. In Table 1, 50°C 2W indicates the results for the damage of test specimens cured at 50°C and 50% relative humidity for two weeks, and 50°C 4W indicates the results for the damage of test specimens cured at 50°C and 50% relative humidity for four weeks. CF: Failure occurs in the cured product (cohesive failure). TCF: Failure has occurred in the hardened material, leaving a thin layer of hardened material on the surface of the mortar board (thin layer cohesive failure). AF: Peeling occurs at the interface between the hardened material and the mortar board (interface failure). If the above-mentioned fracture states are mixed in the test specimen, the fracture states and their percentages (%) are shown in the table.

[0159] Example 2 A curable composition was obtained in the same manner as in Example 1, except that 3-(2-aminoethylamino)propyltrimethoxysilane was not used and the content of each component was changed to the content shown in Table 1. The content of each component in Tables 1 to 3 is shown in parts by weight.

[0160] Example 3 A curable composition was obtained in the same manner as in Example 1, except that polyethyleneimine (SP-006) was replaced with polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin (registered trademark) SP-018) and the content of each component was changed to the content shown in Table 1. The surface tension of polyethyleneimine (SP-018) was calculated in the same manner as in Example 1. The surface tension of polyethyleneimine (SP-018) was 49.3 mN / m.

[0161] Example 4 A curable composition was obtained in the same manner as in Example 3, except that the contents of each component were changed as shown in Table 1.

[0162] Example 5 A curable composition was obtained in the same manner as in Example 2, except that 3-trimethoxysilylpropylsuccinic anhydride was replaced with 3-glycidoxypropyltrimethoxysilane (manufactured by Momentive Performance Materials Japan, LLC, trade name: SILQUEST A-187 SILAN) and the content of each component was changed to the content shown in Table 2. The surface tension of 3-glycidoxypropyltrimethoxysilane was calculated in the same manner as in Example 1. The surface tension of 3-glycidoxypropyltrimethoxysilane was 30.7 mN / m.

[0163] Example 6 A curable composition was obtained in the same manner as in Example 5, except that polyethyleneimine (SP-006) was changed to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin (registered trademark) SP-018).

[0164] Example 7 A curable composition was obtained in the same manner as in Example 1, except that polyethyleneimine (SP-006) was replaced with a modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-161A) having amino groups at both ends of the silicone oil main chain, and the content of each component was changed to the content shown in Table 2. The surface tension of the modified silicone oil was calculated in the same manner as in Example 1. The surface tension of the modified silicone oil was 21.6 mN / m.

[0165] Example 8 A curable composition was obtained in the same manner as in Example 7, except that 3-trimethoxysilylpropylsuccinic anhydride was replaced with 3-glycidoxypropyltrimethoxysilane (manufactured by Momentive Performance Materials Japan, LLC, trade name: SILQUEST A-187 SILAN).

[0166] Example 9 A curable composition was obtained in the same manner as in Example 1, except that 3-trimethoxysilylpropylsuccinic anhydride was not used and the content of each component was changed to the content shown in Table 3.

[0167] Example 10 A curable composition was obtained in the same manner as in Example 7, except that 3-trimethoxysilylpropylsuccinic anhydride was not used and the content of each component was changed to the content shown in Table 3.

[0168] Example 11 A curable composition was obtained in the same manner as in Example 7, except that the modified silicone oil was not used and the content of each component was changed to the content shown in Table 3.

[0169] (Comparative Example 1) A curable composition was obtained in the same manner as in Example 1, except that polyethyleneimine, 3-trimethoxysilylpropylsuccinic anhydride, and 3-(2-aminoethylamino)propyltrimethoxysilane were not used.

[0170] For the curable compositions of Examples 2 to 11 and Comparative Example 1, deep curing properties were measured and mortar adhesion was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0171] [Table 1]

[0172] [Table 2]

[0173] [Table 3]

[0174] Tables 1 to 3 show that the curable compositions of Examples 1 to 11, which contain a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic polymer (B) having a reactive silicon group and use one or more adhesion promoters (C), exhibit good deep curing properties after aging for 16 hours. On the other hand, the cured product of the curable composition of Comparative Example 1, which contained a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic polymer (B) having a reactive silicon group, but did not contain an adhesion promoter (C), exhibited poor deep curing properties after aging for 16 hours.

Claims

1. The composition comprises a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic polymer (B) having a reactive silicon group, and an adhesion promoter (C), the (meth)acrylic polymer (B) contains a structural unit derived from a (meth)acrylic acid alkyl ester, The curable composition, wherein the adhesion promoter (C) has a surface tension of 20 to 110 mN / m, calculated as a value at 23°C according to the Parachor method.

2. 2. The curable composition according to claim 1, wherein the adhesion promoter (C) is at least one selected from the group consisting of polyethyleneimine, silicone oil having reactive groups at both ends, a silane coupling agent having a dicarboxylic anhydride group, and a silane coupling agent having an epoxy group.

3. The curable composition according to claim 1, wherein the adhesion promoter (C) comprises polyethyleneimine and a silane coupling agent having a dicarboxylic acid anhydride group, or comprises polyethyleneimine and a silane coupling agent having an epoxy group.

4. 2. The curable composition according to claim 1, wherein the adhesion promoter (C) comprises a silicone oil having reactive groups at both ends and a silane coupling agent having a dicarboxylic acid anhydride group, or a silicone oil having reactive groups at both ends and a silane coupling agent having an epoxy group.

5. 3. The curable composition according to claim 2, wherein the reactive group is at least one selected from the group consisting of an amino group, a dicarboxylic acid anhydride group, an epoxy group, a reactive silicon group, a hydroxy group, a mercapto group, a carboxy group, and a (meth)acrylic group.

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