Hardening components and hardening agents

Abstract

To provide a curable composition that yields a cured product with a good balance of weather resistance and flexibility, and a cured product of said curable composition. [Solution] A curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic polymer (B) having a reactive silicon group and a structural unit derived from (meth)acrylic acid ester, wherein the (meth)acrylic polymer (B) is used in which the number average molecular weight Mn, the ratio of the weight average molecular weight Mw to Mn Mw / Mn, the glass transition temperature, and the fracture strength of the cured product measured by a specific method are all within predetermined ranges.

Description

[Technical Field]

[0001] The present invention relates to a curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic polymer (B) having a reactive silicon group, and a cured product of said curable composition. [Background Art]

[0002] An organic polymer having at least one reactive silicon group in the molecule can be crosslinked even at room temperature through the formation of siloxane bonds accompanied by hydrolysis reaction of silyl groups caused by moisture or the like. It is known that an organic polymer having a reactive silicon group has the property of providing a rubber-like cured product through such a crosslinking reaction.

[0003] Among organic polymers having a reactive silicon group, polyoxyalkylene polymers having a reactive silicon group are widely used in architectural sealants and industrial sealants. In these applications, long-term excellent weather resistance is required for cured products of curable compositions containing a polyoxyalkylene polymer having a reactive silicon group.

[0004] As a method for improving the weather resistance of cured products, it is known to blend a (meth)acrylic polymer having a reactive silicon group and a polyoxyalkylene polymer having a reactive silicon group in combination into a curable composition (see Patent Document 1). [Prior Art Literature] [Patent Literature]

[0005] [Patent Document 1] International Publication No. WO2014 / 024963 [Summary of the Invention] [Problem to be Solved by the Invention]

[0006] Flexibility is often required for building and industrial sealants. However, conventional curable compositions containing a polyoxyalkylene polymer having reactive silicon groups and a (meth)acrylic polymer having reactive silicon groups, as described in Patent Document 1, make it difficult to achieve both weather resistance and flexibility in the cured product.

[0007] The present invention has been made in view of the above problems, and aims to provide a curable composition that gives a cured product with a good balance of weather resistance and flexibility, and a cured product of the curable composition. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by using a curable composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic polymer (B) having a reactive silicon group and a structural unit derived from (meth)acrylic acid ester, wherein the (meth)acrylic polymer (B) has a number average molecular weight Mn, a weight average molecular weight Mw ratio to Mn Mw / Mn, a glass transition temperature, and a fracture strength of the cured product measured by a specific method, all within predetermined ranges, and have thus completed the present invention.

[0009] More specifically, the present invention provides the following (1) to (4). (1) comprising a polyoxyalkylene polymer (A) having a reactive silicon group, and a (meth)acrylic polymer (B) having a reactive silicon group, The molecular chain of the (meth)acrylic polymer (B) contains constituent units derived from (meth)acrylic acid ester, The number-average molecular weight (Mn) of (meth)acrylic polymer (B), measured by gel permeation chromatography, is 10,000 to 20,000 in polystyrene terms. The ratio of the weight-average molecular weight Mw (in polystyrene terms) to Mn, Mw / Mn, measured by gel permeation chromatography of the (meth)acrylic polymer (B), is 1.6 or higher. The glass transition temperature of the (meth)acrylic polymer (B) is 0°C or lower. The tensile strength of the cured product of (meth)acrylic polymer (B) is 0.020 to 0.300 N / mm². 2 And, Breaking strength is, A mixture is obtained by mixing 100 parts by weight of (meth)acrylic polymer (B) and 2 parts by weight of dibutyltin diacetylacetonate. The mixture is cured to produce a sheet with a thickness of 0.25 ± 0.05 mm. Cut out strip-shaped test pieces with a width of 5 mm from the sheet, and A tensile test will be performed using a test specimen at a tensile speed of 10 mm / min. A curable composition measured by a method comprising the following. (2) Breaking strength is 0.050 to 0.300 N / mm 2 The curable composition described in (1). (3) Breaking strength is 0.050 to 0.200 N / mm 2 The curable composition according to (1) or (2). (4) A cured product of any one of the curable compositions described in (1) to (3). [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a curable composition that gives a cured product with excellent weather resistance and flexibility, and a cured product of the curable composition. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below.

[0012] ≪Curable composition≫ The curable composition comprises a polyoxyalkylene polymer (A) having reactive silicon groups and a (meth)acrylic polymer (B) having reactive silicon groups. The molecular chain of (meth)acrylic polymer (B) contains constituent units derived from (meth)acrylic acid ester. The number-average molecular weight (Mn) of (meth)acrylic polymer (B), measured by gel permeation chromatography in terms of polystyrene, is 10,000 to 20,000. The ratio of the weight-average molecular weight Mw (in polystyrene terms) to Mn, as measured by gel permeation chromatography of the (meth)acrylic polymer (B), is 1.6 or greater (Mw / Mn). The glass transition temperature of (meth)acrylic polymer (B) is 0°C or lower. The tensile strength of the cured product of (meth)acrylic polymer (B) is 0.020 to 0.300 N / mm². 2 That is the case. The above fracture strength is, A mixture is obtained by mixing 100 parts by weight of (meth)acrylic polymer (B) and 2 parts by weight of dibutyltin diacetylacetonate. The mixture is cured to produce a sheet with a thickness of 0.25 ± 0.05 mm. Cut out strip-shaped test pieces with a width of 5 mm from the sheet, and A tensile test will be performed using a test specimen at a tensile speed of 10 mm / min. It is measured by a method consisting of the following:

[0013] The above curable composition provides a cured product that is excellent in weather resistance and also flexible.

[0014] The following describes the essential and optional components that the curable composition may contain.

[0015] <Polyoxyalkylene polymer (A)> The polyoxyalkylene polymer (A) (hereinafter sometimes simply referred to as "polymer (A)") has reactive silicon groups. The reactive silicon group is not particularly limited as long as it is a silicon-containing group having a silanol group or a silicon-containing group that can generate a silanol group by hydrolysis, and may be any known reactive silicon group.

[0016] As the reactive silicon group, the group represented by the following formula (1) is preferred. -SiR 1 a X 3-a (1) In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 is a triorganosiloxy group represented by 3SiO-. In the triorganosiloxy group, the three R 0 are each a hydrocarbon group having 1 to 20 carbon atoms. The three R 0 may be the same or different from each other. X is a hydroxyl group or a hydrolyzable group. a is 0, 1 or 2. R 1 and X, when a plurality of R 1 and a plurality of X are present, the plurality of R and the plurality of X may each be the same or different from each other.

[0017] The polymer (A) has a polymer backbone and polymer chain ends bonded to the polymer backbone. In the specification and claims of the present application, the polymer backbone is also referred to as a "main chain structure". The polymer backbone refers to a structure in which a plurality of constituent units derived from monomers are continuously bonded. The monomers may be of one type or a plurality of types.

[0018] The polymer chain end is a site 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 is 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.

[0019] Reactive silicon groups may be present in the polymer backbone and in the polymer chain ends. Also, two or more reactive silicon groups may be present in one polymer chain end. When the curable composition is used in adhesives, sealing materials, elastic coating agents, pressure-sensitive adhesives and the like, it is preferable that the reactive silicon groups in the polymer (A) are present in the polymer chain ends.

[0020] (Reactive silicon group) A reactive silicon group is a group that has a silanol group or a group that can generate a silanol group by hydrolysis. When a reactive silicon group generates a silanol group, polymer (A) is crosslinked by a condensation reaction between the silanol groups. As mentioned above, the reactive silicon group is preferably the group represented by formula (1) above.

[0021] R in equation (1) 1 Specific examples 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 groups and aryl groups are preferred, methyl, ethyl, and phenyl groups are more preferred, methyl and ethyl groups are even more preferred, and methyl groups are particularly preferred. 1 If multiple R 1 These may be the same group, or a combination of two or more different groups.

[0022] In formula (1), X is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be any known hydrolyzable group. Specific examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenyloxy groups are preferred, and alkoxy groups such as methoxy groups and ethoxy groups are more preferred because they are mildly hydrolyzable and easy to handle. Methoxy groups are preferred because they allow for easy adjustment of the curability of the curable composition.

[0023] 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 group, diethoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group, dimethoxyphenylsilyl group, methoxymethyldimethoxysilyl group, methoxymethyldiethoxysilyl group, triisopropenyloxysilyl group, and triacetoxysilyl group. Among these, the dimethoxymethylsilyl group and the trimethoxysilyl group are preferred because they facilitate the synthesis of polymer (A). The trimethoxysilyl group and the methoxymethyldimethoxysilyl group are preferred because they exhibit excellent curability. The dimethoxymethylsilyl group is particularly preferred because of its excellent stability.

[0024] (Regarding the main chain structure of polymer (A)) Polymer (A) is a polyoxyalkylene polymer. Therefore, the main chain structure of the polymer consists of a polyoxyalkylene polymer. Specifically, the main chain structure of polymer (A) can be made of polyoxyalkylene polymers such as polyoxyethylene polymer, polyoxypropylene polymer, polyoxybutylene polymer, polyoxytetramethylene polymer, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer.

[0025] Because it exhibits excellent deep curing properties as a one-component composition, and also has excellent adhesive properties, polyoxypropylene is preferred as the main chain structure among polyoxyalkylene polymers.

[0026] Polyoxyalkylene polymers are -R 3 It is a polymer having repeating units represented by -O-. 3 R is a linear or branched alkylene group having 1 to 14 carbon atoms. 3 As such, linear or branched alkylene groups having 2 to 4 carbon atoms are more preferred. -R 3Specific examples of repeating units represented by -O- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-. The main chain structure of a polyoxyalkylene polymer may consist of only one type of repeating unit or of two or more types of repeating units. In particular, when the curable composition is used as a sealant, adhesive, etc., a polyoxypropylene polymer having 50% or more, preferably 80% or more by weight of oxypropylene repeating units in the polymer main chain structure is preferred as the polyoxyalkylene polymer. This is because such a polyoxyalkylene polymer is amorphous and has relatively low viscosity.

[0027] The main chain structure of the polyoxyalkylene polymer may be linear or branched.

[0028] As for polyoxyalkylene polymers, polymers obtained by a ring-opening polymerization reaction of cyclic ether compounds using a polymerization catalyst in the presence of an initiator are preferred.

[0029] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used individually or in combination of two or more. Among these cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous and relatively low-viscosity polyether polymers.

[0030] Specific examples of initiators 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 polyoxypropylenediol, polyoxypropylenetriol, polyoxyethylenediol, and polyoxyethylenetriol.

[0031] The method for synthesizing polyoxyalkylene polymers is not particularly limited. Examples of synthesis methods for polyoxyalkylene polymers include polymerization using alkaline catalysts such as KOH, polymerization using transition metal compound-porphyrin complex catalysts such as the complex obtained by reacting an organoaluminum compound with porphyrin as shown in Japanese Patent Publication No. 61-215623, polymerization using complex metal cyanide complex catalysts as shown in Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, U.S. Patent No. 3278457, U.S. Patent No. 3278458, U.S. Patent No. 3278459, U.S. Patent No. 3427256, U.S. Patent No. 3427334, and U.S. Patent No. 3427335, etc., polymerization using catalysts consisting of polyphosphazene salts as exemplified in Japanese Patent Publication No. 10-273512, and polymerization using catalysts consisting of phosphazene compounds as exemplified in Japanese Patent Publication No. 11-060722. Polymerization using complex metal cyanide catalysts is more preferable due to reasons such as lower manufacturing costs and the ability to obtain polymers with a narrow molecular weight distribution.

[0032] The main chain structure of polymer (A) may be a polyoxyalkylene polymer containing urethane bonds and other bonds other than ether bonds, such as urea bonds, to the extent that the desired effect is not significantly impaired. Specific examples of polymers having such a main chain structure include polyurethane prepolymers and polyurea prepolymers.

[0033] Polyurethane prepolymers can be obtained by known methods, such as reacting a polyol compound with a polyisocyanate compound. Polyurea prepolymers can be obtained by known methods, such as reacting a polyamine compound with a polyisocyanate compound. The main chain structure may be a prepolymer having a combination of urethane and urea bonds, obtained by reacting a polyol compound and a polyamine compound with a polyisocyanate compound.

[0034] Specific examples of polyol compounds include polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.

[0035] Specific examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.

[0036] The ends of the polyurethane prepolymer may be either hydroxyl groups or isocyanate groups. The ends of the polyurea prepolymer may be either amino groups or isocyanate groups.

[0037] In curable compositions containing polymer (A) having one or more bonds selected from urethane bonds, urea bonds, and ester bonds in its main chain structure, the strength of the cured product may decrease due to cleavage of the urethane bonds, urea bonds, or ester bonds in the main chain structure caused by heat or other factors.

[0038] When polymers containing amide bonds in their main chain structure are used as organic polymers, the curability of the curable composition may be improved. For example, amide bonds can be represented as -NR. 4 It is represented as -C(=O)- R 4This is an organic group that may have a hydrogen atom or 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 the decrease in strength of the cured product due to cleavage of amide bonds due to heat, etc., and the increase in viscosity of the curable composition due to storage are less likely to occur, resulting in good workability of the curable composition.

[0039] When polymer (A) contains amide bonds in its main chain structure, the number of amide bonds is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 3, on average per molecule. When the number of amide bonds on average per molecule is within this range, the curability of the curable composition is good, the viscosity of polymer (A) is low, and both polymer (A) and the curable composition are easy to handle.

[0040] Of the polymers (A) described above, polyoxyalkylene polymers that do not contain urethane bonds, urea bonds, ester bonds, or amide bonds in their main chain structure are most preferred, in terms of obtaining a curable composition with excellent storage stability and workability.

[0041] As polymer (A), a polymer obtained by introducing reactive silicon groups into the polymer by any of the following methods (a) to (d) is preferred. (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups are converted to HSiR 1 a X 3-a A method of hydrosilylation using a hydrosilane represented by R. 1 X and a are the same as those in equation (1), respectively. (b) OCN-W-SiR 1 a X 3-a A method for reacting an isocyanate alkylsilane compound represented by . W is a divalent organic group. R 1 X and a are the same as those in equation (1), respectively. (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 a X 3-a A method for carrying out an en-thiol reaction with a mercaptoalkylsilane compound represented by . W is a divalent organic group. R 1 X and a are the same as those in equation (1), respectively. (d) After synthesizing an NCO group-terminated organic polymer by reacting a hydroxyl group-terminated organic polymer with a polyisocyanate compound, the terminal NCO group is HNR 5 -W-SiR 1 a X 3-a , or HS-W-SiR 1 a X 3-a A method of reacting with a silane compound represented by . W is a divalent organic group. R 5 R is a hydrogen atom or an alkyl group. 1 X and a are the same as those in equation (1), respectively.

[0042] In the methods described in (a) and (c) above, examples of terminal carbon-carbon unsaturated groups include vinyl groups, allyl groups, methallyl groups, allenyl groups, and propargyl groups.

[0043] In any of the methods (b) to (d) above, the polymer (A) obtained using a silane compound in which W is methylene exhibits very high curability.

[0044] Method (a) is preferred because it is easy to obtain polymer (A) which has good storage stability. Methods (b), (c), and (d) are preferred because a high conversion rate can be obtained with a relatively short reaction time.

[0045] Methods for introducing reactive silicon groups by method (a) are proposed in the following publications: Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Publication Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Patent No. 3632557, U.S. Patent No. 4345053, U.S. Patent No. 4366307, and U.S. Patent No. 4960844. Examples include the methods described, or the methods proposed in Japanese Patent Publication Nos. 61-197631, 61-215622, 61-215623, and 61-218632, which introduce reactive silicon groups to a high molecular weight polyoxypropylene polymer with a number average molecular weight of 6,000 or more, an Mw / Mn ratio of 1.6 or less, and a narrow molecular weight distribution, by hydrosilylation, etc., or the method proposed in Japanese Patent Publication No. 3-72527. Furthermore, as a method for introducing more than one reactive silicon group at the molecular end, the method proposed in Japanese Patent No. 6096320 can be cited.

[0046] The number-average molecular weight (Mn) of polymer (A) is not particularly limited. The number-average molecular weight of polymer (A) is preferably 5,000 to 40,000, and more preferably 6,000 to 30,000, as polystyrene-equivalent molecular weight in gel permeation chromatography (GPC).

[0047] The molecular weight of polymer (A) can also be expressed as the end-group-reduced molecular weight, obtained by directly measuring the end-group concentration of the polymer precursor before the introduction of reactive silicon groups using 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 considering the structure of the polymer (degree of branching determined by the polymerization initiator used). Alternatively, the end-group-reduced molecular weight of polymer (A) can be determined by creating a calibration curve between the number-average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned end-group-reduced molecular weight, and then converting the number-average molecular weight obtained by GPC of polymer (A) to the end-group-reduced molecular weight.

[0048] The molecular weight distribution (Mw / Mn) of polymer (A) is not particularly limited. A narrow molecular weight distribution of polymer (A) is preferred. 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 polymer (A) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0049] To obtain a good rubber-like cured product, it is preferable that the reactive silicon groups of polymer (A) are present at the ends of the polymer chains. The number of reactive silicon groups is preferably 0.5 or more and 3.0 or less on average per polymer chain end, 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 polymer (A) and the curable composition is good, and the cured product of the curable composition has good rubber elasticity.

[0050] 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.

[0051] Furthermore, as described in Publication No. WO2013 / 180203, organic polymers having two or more reactive silicon groups at the ends of the polymer chains can also be used as polymer (A). Such polymers (A) exhibit high curability, and the resulting cured product can be expected to have high strength and high resilience.

[0052] Specific examples of commercially available polymer (A) products include Kaneka MS Polymer (registered trademark) and various reactive silicon group-containing polyoxypropylene products such as Kaneka Cyril (registered trademark). All of these commercially available polymers (A) are products of Kaneka Corporation. In addition, AGC Inc.'s Exester (registered trademark), WACKER's GENIOSIL (registered trademark), and RISUN POLYMER's STP can also be used.

[0053] <(meth)acrylic polymer (B)> (Meth)acrylic polymer (B) (hereinafter sometimes simply referred to as "polymer (B)") has reactive silicon groups. The reactive silicon group is not particularly limited as long as it can form a siloxane bond. The reactive silicon group represented by formula (1) above is preferred. Polymer (B) has a polymer skeleton and polymer chain ends bonded to the polymer skeleton. The polymer skeleton is a structure in which multiple structural units derived from monomers are continuously bonded. There may be one or more types of monomers.

[0054] Polymer chain ends are the parts located at the ends of polymer (B). The number of polymer chain ends in polymer (B) is 2 if the main chain structure is linear.

[0055] Reactive silicon groups can be present in the polymer backbone and at the polymer chain ends. When using a curable composition in adhesives, sealants, elastic coatings, or other adhesives, it is preferable that the reactive silicon groups are present at the polymer chain ends in polymer (B).

[0056] The reactive silicon groups of polymer (B) may be the same as or different from the reactive silicon groups of polymer (A).

[0057] (Regarding the main chain structure of polymer (B)) Polymer (B) contains constituent units derived from (meth)acrylic acid esters.

[0058] (Meth)acrylate alkyl ester means alkyl acrylate and / or alkyl methacrylate. Specific examples of alkyl acrylates 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, and stearyl acrylate, behenyl acrylate, and others.

[0059] Specific examples of alkyl methacrylates 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.

[0060] The ratio of the weight of constituent units derived from (meth)acrylic acid ester to the weight of polymer (B) is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

[0061] From the viewpoint of the compatibility of polymer (B) with polymer (A) and the stability of polymer (B), the alkyl (meth)acrylate ester used to prepare polymer (B) is preferably an alkyl (meth)acrylate ester having an alkyl group with 1 to 30 carbon atoms.

[0062] Alkyl (meth)acrylate esters having an alkyl group with 1 to 30 carbon atoms are defined by the following formula (B1): CH2=CR b1 COOR b2 (B1) (In formula (B1), R b1 R is a hydrogen atom or a methyl group. b2 (These are alkyl groups with 1 to 30 carbon atoms.) It is represented as follows.

[0063] In equation (B1), R b2 Examples include alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, 2-ethylhexyl group, lauryl group, n-tridecyl group, cetyl group, and stearyl group. R b2 The number of carbon atoms in the alkyl group is more preferably 1 to 20.

[0064] The monomers used to produce polymer (B) may include monomers other than alkyl (meth)acrylate. 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; epoxyalkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate; acrylonitrile and methacrylonitrile; styrenes such as styrene and α-methylstyrene; alkyl vinyl ethers; vinyl chloride; fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

[0065] The number-average molecular weight of polymer (B) is preferably 10,000 to 20,000, and more preferably 12,000 to 18,000, as polystyrene-based molecular weight in GPC. The weight-average molecular weight (Mw) of polymer (B) is preferably 16,000 to 80,000, and more preferably 20,000 to 60,000, as the polystyrene-equivalent molecular weight in GPC.

[0066] The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight Mw of polymer (B) to Mn, is not particularly limited. A narrow molecular weight distribution of polymer (B) is preferred. Specifically, the molecular weight distribution is preferably 1.6 or higher, more preferably 2.0 or higher, and even more preferably 2.4 or higher. The upper limit of the molecular weight distribution (Mw / Mn) may be, for example, 4.0 or lower, or 3.5 or lower. The molecular weight distribution of polymer (B) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0067] Polymer (B) can be produced by conventional vinyl polymerization methods. Examples of vinyl polymerization methods include solution polymerization by radical reaction and bulk polymerization. However, vinyl polymerization methods are not limited to these methods. The polymerization reaction described above is typically carried out at 50-150°C in the presence of monomers, radical initiators, chain transfer agents, and solvents. The conditions for the polymerization reaction are not limited to those described above.

[0068] Specific examples of radical initiators include azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and benzoyl peroxide. Specific examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan, as well as halogen-containing compounds. As solvents, solvents that are inert to polymerization reactions, such as ethers, hydrocarbons, and esters, can preferably be used.

[0069] Various methods are known for introducing reactive silicon groups into (meth)acrylic polymers. For example, I) A method for copolymerizing a compound having an ethylenically unsaturated double bond and a reactive silicon group with an alkyl (meth)acrylate represented by formula (B1); II) A copolymer obtained by copolymerizing a compound having an ethylenically unsaturated double bond and a reactive functional group (e.g., acrylic acid) with an alkyl (meth)acrylate represented by formula (B1), wherein the reactive functional group 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 for polymerizing an alkyl (meth)acrylate represented by formula (B1) in the presence of a mercaptan having a reactive silicon group as a chain transfer agent; VI) A method for polymerizing an alkyl (meth)acrylate 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) One method involves introducing reactive silicon groups at the end of the molecular chain in a polymer obtained by polymerizing an alkyl (meth)acrylate represented by formula (B1) using living radical polymerization, but it is also possible to combine at least two of the methods I), II), and III). The method for introducing reactive silicon groups into (meth)acrylic polymers is not limited to the above methods, but I), II), III), a combination of I) and III), II) and III) are preferred, and I), III), a combination of I) and III) is more preferred.

[0070] The compound having an ethylenically unsaturated double bond and a reactive silicon group used in the method described in I) above is the following formula (B2): CH2=CR b5 COOR b6 -SiR 1 a X 3-a (B2) (In formula (B2), R 1 , X, and a are R in equation (1) 1 , X, and a are the same. b5 R is a hydrogen atom or a methyl group. b6 (This refers to an alkylene group with 1 to 6 carbon atoms.) Compounds represented by are preferred.

[0071] In equation (B2), R b6 The alkylene group 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 preferably an alkylene group having 1 to 4 carbon atoms.

[0072] Specific examples of compounds having an ethylenically unsaturated double bond and a reactive silicon group include γ-methacryloxypropyl alkoxysilanes such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane; γ-acryloxypropyl alkoxysilanes such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltriethoxysilane; and vinyl alkoxysilanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane.

[0073] Examples of reactive functional groups in compounds having an ethylenically unsaturated double bond and a reactive functional group used in method II) above include amino groups, hydroxyl groups, and carboxyl groups. Examples of groups that can react with these reactive functional groups include isocyanate groups. Furthermore, as described in other publications such as Japanese Patent Publication No. 54-36395, Japanese Patent Publication No. 01-272654, and Japanese Patent Publication No. 02-214759, allyl groups can be used as reactive functional groups. Silicon hydride (H-Si) groups can react with allyl groups.

[0074] Examples of mercaptans containing reactive silicon groups as chain transfer agents used in method III) above include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0075] Examples of azobisnitrile compounds and disulfide compounds having a reactive silicon group used in the method described in IV) above include azobisnitrile compounds having an alkoxysilyl group and disulfide compounds having an alkoxysilyl group as described in Japanese Patent Publication No. 60-23405 and Japanese Patent Publication No. 62-70405, etc.

[0076] An example of the method described in (V) above is the method described in Japanese Patent Publication No. 09-272714, etc.

[0077] Other methods include those described in Japanese Patent Publication No. 59-168014 and Japanese Patent Publication No. 60-228516, which involve the combined use of a mercaptan having a reactive silicon group and a radical polymerization initiator having a reactive silicon group.

[0078] The tensile strength of the cured polymer (B) is 0.020 to 0.300 N / mm². 2 The range is 0.050~0.300 N / mm². 2 Preferably, the value is 0.050 to 0.200 N / mm². 2 It is more preferable that the tensile strength of the cured polymer (B) is 0.020 to 0.300 N / mm². 2 As a result, the cured product of the composition obtained by mixing polymer (B) and polymer (A) has high weather resistance and also possesses flexibility. Furthermore, if the tensile strength is excessively high, for example, the elongation at break tends to decrease, and the flexibility of the cured product of the curable composition tends to decrease.

[0079] The tensile strength of the cured polymer (B) is measured by the following method. The method for measuring the fracture strength of a cured polymer (B) is: Polymer (B) is obtained by mixing 100 parts by weight of acrylic polymer (B) with 2 parts by weight of dibutyltin diacetylacetonate. The mixture is cured to produce a sheet with a thickness of 0.25 ± 0.05 mm. Cut out strip-shaped test pieces with a width of 5 mm from the sheet, and A tensile test will be performed using a test specimen at a tensile speed of 10 mm / min. It consists of.

[0080] The method for adjusting the tensile strength of the cured polymer (B) measured by the above method is not particularly limited. For example, increasing the amount of constituent units having reactive silicon groups in polymer (B) tends to increase the tensile strength. Also, increasing the Tg of polymer (B) tends to increase the tensile strength.

[0081] The amount of polymer (B) used in the curable composition is not particularly limited, as long as the desired effect is not impaired. In a curable composition, the weight W of the polyoxyalkylene polymer (A) A And the weight W of (meth)acrylic resin (B) B The ratio W A / W B However, 95 / 5 to 5 / 95 is preferred, 90 / 10 to 20 / 80 is more preferred, and 80 / 20 to 30 / 70 is even more preferred.

[0082] The glass transition temperature (Tg) of polymer (B) is 0°C or lower, more preferably -80 to -10°C, and even more preferably -60 to -20°C. The Tg can be determined using Fox's formula shown below.

[0083] Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi is the weight fraction of monomer i that constitutes the polymer, and Tgi is the glass transition temperature (K) of the homopolymer of monomer i.)

[0084] <Other additives> The curable composition may contain other additives in addition to polymer (A) and polymer (B), as long as the desired effect is not impaired. Examples of other additives include curing catalysts, fillers, adhesion promoters, plasticizers, solvents, diluents, thixotropic agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, epoxy resins, other resins, surface modifiers, foaming agents, curing modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0085] (curing catalyst) The curable composition preferably contains a curing catalyst for the purpose of promoting the hydrolysis condensation reaction between the reactive silicon groups of polymer (A) and polymer (B), thereby extending or crosslinking the polymer chains.

[0086] Examples of curing catalysts include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, and alkoxy metals.

[0087] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin diacetylacetonate, dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reaction products of dibutyltin oxide and silicate compounds, reaction products of dioctyltin oxide and silicate compounds, and reaction products of dibutyltin oxide and phthalate esters.

[0088] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate. Furthermore, salts combining the following carboxylic acids with various metals can be used as metal carboxylate salts.

[0089] Specific examples of amine compounds 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 butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0090] 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.

[0091] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), and diisopropoxytitanium bis (ethylacetoacetate), as well as 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. The curing catalyst may be used in combination of two or more different catalysts. The amount of curing 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, based on 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0092] (Filler) Various fillers may be added to the curable composition. Examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, and carbon black; fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum powder, flint powder, zinc oxide, activated zinc oxide, and resin powder; and fibrous fillers such as asbestos, glass fibers, and filaments. Examples of resin powders include PVC powder and PMMA powder. When using a filler, the amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 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).

[0093] When a hardened product with high strength is desired using these fillers, fillers selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide are preferably used. In terms of the strength of the cured product, the preferred amount of these fillers to use is 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, if it is desired to obtain a cured product with low strength and high elongation at break, fillers selected mainly from titanium dioxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons can be preferably used. In terms of the elongation at break of the cured product, the preferred amount of these fillers to use is 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).

[0094] The curable composition may contain spherical hollow bodies, such as balloons, for the purpose of reducing the weight (specific gravity) of the cured product. A balloon is a hollow, spherical filler. Examples of balloon materials include inorganic materials such as glass, shirasu (volcanic ash), and silica, and organic materials such as phenolic resin, urea resin, polystyrene, saran, and acrylonitrile. However, the balloon material is not limited to these materials. The balloon material may be a composite material consisting of inorganic and organic materials. Furthermore, the balloon material may consist of multiple layers laminated together. In addition, a single type of balloon may be used, 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 dioxide, etc., or inorganic balloons surface-treated with silane coupling agents can be used.

[0095] 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 weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). The lower limit is more preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. Using an amount of spherical hollow bodies within the above range results in a good curable composition and makes it easy to form a cured product with excellent elongation and tensile strength.

[0096] (Adhesion-enhancing agent) The curable composition may contain an adhesion promoter. An example of an adhesion promoter is a silane coupling agent. Silane coupling agents are compounds having a hydrolyzable silicon group and a functional group other than a hydrolyzable silicon group in their molecule. When a silane coupling agent is used, a curable composition is applied to various substrates, including inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, and polycarbonate, resulting in a significant improvement in adhesion under non-primer conditions or primer-treated conditions. The effect of improving adhesion to various substrates is particularly pronounced when the curable composition is used under non-primer conditions.

[0097] The hydrolyzable groups in the hydrolyzable silicon groups of the silane coupling agent are 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, with methoxy groups and ethoxy groups being particularly preferred, due to their mild hydrolysis and ease of handling. Furthermore, ethoxy groups and isopropenyloxy groups are preferred in terms of safety because the compounds eliminated by the reaction are ethanol and acetone, respectively. The number of hydrolyzable groups bonded to the silicon atoms in the silane coupling agent may be preferably three to ensure good adhesion. Alternatively, two may be preferable to ensure the storage stability of the curable composition.

[0098] Specific examples of aminosilane coupling agents 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 amino group-containing silanes include 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-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine.

[0099] Of these, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, and 3-(2-aminoethylamino)propylmethyldimethoxysilane are preferred in terms of good adhesion of the cured product. One aminosilane coupling agent may be used, or two or more may be used in combination. It has been noted that 3-(2-aminoethylamino)propyltrimethoxysilane is more irritating than other aminosilanes. Irritation can be mitigated by reducing the amount of 3-(2-aminoethylamino)propyltrimethoxysilane and using 3-aminopropyltrimethoxysilane in combination. Furthermore, silane coupling agents oligomerized by partially condensing hydrolyzable silicon groups can also be suitably used in terms of safety and stability. The silane coupling agents to be condensed may be a single agent or multiple agents. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. In terms of good storage stability of the curable composition, 3-aminopropyltrimethoxysilane and 3-(2-aminoethylamino)propylmethyldimethoxysilane are preferred.

[0100] Specific examples of silane coupling agents other than aminosilane coupling agents include epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropylmethyldiethoxysilane, 3-isocyanatetopropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane; and 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane. Examples include mercapto group-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; carboxysilane coupling agents such as 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-2-(carboxymethylamino)ethyl-3-aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-acryloyloxypropylmethyltriethoxysilane; halogen-containing silane coupling agents such as 3-chloropropyltrimethoxysilane; and isocyanurate silane coupling agents such as tris(trimethoxysilyl)isocyanurate. In addition, condensates obtained by partially condensing the above silane coupling agents can also be used. Examples of such condensates include Dynasylan6490 and Dynasylan6498 from Evonik.Furthermore, modified derivatives of these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0101] Of these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane are preferred in terms of good adhesion of the cured product.

[0102] The above silane coupling agents may be used individually or in combination of two or more types. The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, and 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).

[0103] (Plasticizer) The curable composition may contain a plasticizer. By adding a plasticizer, the viscosity and slump of the curable composition, as well as the mechanical properties of the cured product, such as tensile strength and elongation, can be adjusted.

[0104] 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 ester 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, and disuccinate. Examples include aliphatic polycarboxylic acid ester compounds such as isodecyl and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate. A specific example of a terephthalate ester compound is EASTMAN 168 (trade name, manufactured by EASTMAN CHEMICAL). A specific example of a non-phthalate ester compound is Hexamoll DINCH (trade name, manufactured by BASF). A specific example of an alkylsulfonate phenyl ester is Mesamoll (trade name, manufactured by LANXESS).

[0105] High molecular weight plasticizers can also be used. Using high molecular weight plasticizers allows the initial properties of the cured product to be maintained over a longer period compared to using low molecular weight plasticizers. Furthermore, the drying properties (coatability) when alkyd paint is applied to the cured product are improved.

[0106] 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 with a number average molecular weight of 500 or more, and even 1,000 or more; derivatives of these polyether polyols obtained by converting the hydroxyl groups to ester groups, ether groups, etc.; polystyrenes such as polystyrene and poly-α-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Polymeric plasticizers are not limited to these.

[0107] The polymeric plasticizer is preferably compatible with polyoxyalkylene polymers (A) and / or (meth)acrylic polymers (B). From this point of view, 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 also preferred from the viewpoint of compatibility with polyoxyalkylene polymers (A) and / or (meth)acrylic polymers (B), as well as 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 alkyl polyacrylates are even more preferred. As for the synthesis method of vinyl polymers, living radical polymerization is preferred, and atom transfer radical polymerization is even more preferred, as it yields polymers with a narrow molecular weight distribution and low viscosity. Furthermore, the so-called SGO process, described in Japanese Patent Publication No. 2001-207157, which involves continuous bulk polymerization of alkyl acrylate monomers at high temperature and high pressure, is also a preferred method for producing vinyl polymers.

[0108] The number-average molecular weight of the polymeric plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, even 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 polymeric plasticizer is within the above range, the leaching of the plasticizer from the cured product over time due to heat, rainfall, etc., can be suppressed, the initial physical properties of the cured product can be maintained for a long period of time, the curable composition has an appropriate viscosity, and the curable composition has good workability.

[0109] The number-average molecular weight of vinyl polymers is measured by GPC (Gross Propagation). The number-average molecular weight of polyether polymers is measured by end-group analysis.

[0110] The polymeric plasticizer may or may not have reactive silicon groups. If the polymeric plasticizer has reactive silicon groups, it acts as a reactive plasticizer, preventing the migration of the plasticizer from the cured product. When the polymeric plasticizer has reactive silicon groups, the number of reactive silicon groups is preferably one or less on average per molecule, and more preferably 0.8 or less. When using a plasticizer having reactive silicon groups, particularly a polyether polymer having reactive silicon groups, its number-average molecular weight must be lower than the number-average molecular weight of the polyoxyalkylene polymer (A) and / or the (meth)acrylic polymer (B).

[0111] Among the plasticizers described above, at least one selected from the group consisting of phthalate esters, hydrogenated phthalate esters, and polyoxyalkylene compounds is preferred.

[0112] 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 form a cured product with excellent mechanical strength while fully obtaining the desired effect of using the plasticizer. The plasticizer may be used alone or in combination of two or more types. A low molecular weight plasticizer and a high molecular weight plasticizer may be used in combination. These plasticizers may be blended into the polyoxyalkylene polymer (A) or the (meth)acrylic polymer (B) when producing the polyoxyalkylene polymer (A) or the (meth)acrylic polymer (B).

[0113] (Solvents, diluents) The curable composition may contain a solvent or a diluent. The solvent and diluent are not particularly limited. Examples of solvents and diluents include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When using a solvent or diluent, to address the issue of air pollution when the curable composition is used indoors, 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. The solvent or diluent may be used alone or in combination of two or more.

[0114] (Tixotropic agent) The curable composition may contain a thixotropic agent as needed to prevent sagging and improve workability. The thixotropic agent is not particularly limited. Examples of thixotropic agents include polyamide waxes and hydrogenated castor oil derivatives. These thixotropic agents may be used alone or in combination of two or more. The amount of thixotropic agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0115] (Antioxidant) The curable composition may contain an antioxidant (anti-aging agent). Using 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. For example, 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 are examples of suitable antioxidants. Similarly, hindered amine-based light stabilizers such as Chinuvin 622LD, Chinuvin 144, Chinuvin 292, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by BASF); Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, and Adekastab LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Life Tech Co., Ltd.); and Nocrack CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants such as SONGNOX4120, Nowguard445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731. The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0116] (Light stabilizer) The curable composition may contain a light stabilizer. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds. The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). Specific examples of light stabilizers are described, for example, in Japanese Patent Publication No. 9-194731.

[0117] (UV absorber) The curable composition may contain an ultraviolet absorber. Using an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, triazine compounds, substituted tolyl compounds, and metal chelate compounds. Among these, benzotriazole compounds are particularly preferred. Specific examples of benzotriazole compounds include tinubine 234, tinubine 326, tinubine 327, tinubine 328, tinubine 329, tinubine 350, tinubine 571, tinubine 900, tinubine 928, tinubine 1130, tinubine 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 UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B). It is preferable to use a combination of a phenolic antioxidant or a hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole UV absorber. AddworksIBC760 (manufactured by Clariant) can be used as a product containing antioxidants, light stabilizers, and UV absorbers.

[0118] (Property modifier) The curable composition may optionally contain a property modifier to adjust the tensile properties of the cured product. The property modifier is not particularly limited. Examples of property modifiers 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-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. By using property modifiers, it is possible to increase the hardness of the cured product or, conversely, decrease its hardness and increase its elongation at break. The above property modifiers may be used alone or in combination of two or more types.

[0119] In particular, compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis have the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Among the compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis, compounds that produce trimethylsilanol are particularly preferred. Examples of compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis include the compounds described in Japanese Patent Publication No. 5-117521. In addition, examples of compounds that produce trialkylsilanols such as trimethylsilanol upon hydrolysis include derivatives of alkyl alcohols such as hexanol, octanol, and decanol, and derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol, or sorbitol, which produce trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in Japanese Patent Publication No. 11-241029. Examples include derivatives of oxyalkylene polymers that produce silicon compounds that generate trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in Japanese Patent Publication No. 7-258534. Furthermore, polymers having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can become a monosilanol-containing compound upon hydrolysis, as described in Japanese Patent Publication No. 6-279693, can also be used. The property modifier 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 weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0120] (Adhesive-forming resin) The curable composition may contain a tackifying resin for purposes such as improving the adhesion and bonding of the cured product to the substrate. There are no particular restrictions on the tackifying resin, and any tackifying resin commonly used in various curable compositions can be used. Specific examples of tackifying resins include terpene resins, aromatically modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, 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 individually or in combination of two or more types. The amount of tackifying 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 tackifying resin within this range allows for the formation of a cured product with good adhesion and bonding to the substrate. The curable composition has an appropriate viscosity and is easy to handle.

[0121] (Compounds containing epoxy groups) The curable composition may contain compounds containing epoxy groups. Using compounds with epoxy groups can improve the resilience of the cured product. Examples of compounds with epoxy groups include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples of compounds with epoxy groups include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, and epoxybutyl stearate. The amount of epoxy group-containing compound used is preferably 0.5 to 50 parts by weight per 100 parts by weight of the total weight of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B).

[0122] (Epoxy resin) The curable composition may contain an epoxy resin. Curable compositions containing an epoxy resin are preferred as adhesives, particularly as adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins. The ratio of the total weight of polyoxyalkylene polymer (A) and (meth)acrylic polymer (B) to the weight of epoxy resin is preferably in the range of 100 / 1 to 100 / 100, expressed as (weight of polymer (A) and polymer (B)) / (weight of epoxy resin). When polymer (A) and polymer (B) and epoxy resin are used in the above ratio, it is easy to form a high-strength cured product with excellent impact strength and toughness. When using epoxy resin, the curing composition may contain a curing agent along with the epoxy resin. The type of curing agent is not particularly limited, and commonly used curing agents can be used. The amount of hardener used is preferably 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0123] (light curing substance) The curable composition may contain a photocurable substance. Using a photocurable substance forms a film of the photocurable substance 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. Numerous compositions containing photocurable substances are also known. Representative photocurable substances include unsaturated acrylic compounds, polyvinyl polycinnamates, and azidized resins. Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups. The amount of photocurable material used is preferably 0.1 to 20 parts by weight, and 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). When an amount of photocurable material within this range is used, it is easy to form a flexible cured product with excellent weather resistance and suppressed cracking.

[0124] (oxygen curing substance) The curable composition may contain an oxygen-curable substance. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. When the curable composition contains an oxygen-curable substance, the oxygen-curable 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-curable 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 individually or in combination of two or more. The amount of oxygen-curable substance used is preferably 0.1 to 20 parts by weight, and 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 that is less susceptible to contamination by dirt and dust on the surface and has excellent mechanical properties such as tensile strength. As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0125] Preparation of curable compositions The curable composition can be prepared as a one-component type, where all components are pre-mixed and sealed for storage, and then cured by moisture in the air after application. Alternatively, a curing agent such as a curing catalyst, filler, plasticizer, and water can be separately added, and the mixture can be mixed with a polymer composition containing a polyoxyalkylene polymer (A) and a (meth)acrylic polymer before use to prepare a two-component type. From the viewpoint of workability, a one-component type is preferred.

[0126] When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable that components containing water be dehydrated and dried before use, or that they be dehydrated during mixing by reduced pressure or other means. In addition to the dehydration drying method, the storage stability of the curable composition is further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane to the curable composition.

[0127] Uses of curable compositions Curable compositions can be used as sealants, industrial adhesives, waterproof coating compositions, and adhesive raw materials. They can also be used as sealants for buildings, ships, automobiles, and roads. Furthermore, curable compositions can adhere to a wide range of substrates, including glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer. Therefore, curable compositions can be used as various types of sealing and adhesive compositions. In addition to being ordinary adhesives, curable compositions can also be used as contact adhesives. Moreover, curable compositions are useful as food packaging materials, casting rubber materials, molding materials, and paints. [Examples]

[0128] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0129] (molecular weight) The number-average molecular weight Mn and weight-average molecular weight Mw in the examples are GPC molecular weights measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0130] (Average number of reactive silicon groups) The average number of reactive silicon groups per molecule of the polymers shown in the examples was calculated by NMR measurement.

[0131] (Glass transition temperature Tg) The glass transition temperature Tg was determined using Fox's formula below. Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of monomer i that constitutes the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of monomer i.)

[0132] [Synthesis Example 1] Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene (P-1) with a number-average molecular weight of 27,900 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, having hydroxyl groups at both ends. Subsequently, 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (P-1). After removing methanol by vacuum defoliation, an additional 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups, and the unreacted allyl chloride was removed by vacuum defoliation. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. From the above steps, polyoxypropylene (Q-1) having allyl groups at its termini was obtained. To 500 g of this polymer (Q-1), 50 μL of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added, and 4.8 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting the mixed solution at 100°C for 2 hours, the unreacted dimethoxymethylsilane was removed under reduced pressure to obtain polyoxypropylene (A-1) with dimethoxymethylsilyl groups at its termini and a number-average molecular weight of approximately 28,500. Polymer (A-1) was found to have an average of 0.8 dimethoxymethylsilyl groups at each termini and an average of 1.6 dimethoxymethylsilyl groups per molecule.

[0133] [Synthesis Example 2] To 81.4 g of isobutyl alcohol (IBA) heated to 105°C in a reaction vessel, a solution of 6.2 g of azobis-2-methylbutyronitrile dissolved in a mixture of 34.3 g of methyl methacrylate, 188.7 g of butyl acrylate, 44.6 g of 2-ethylhexyl acrylate, 68.6 g of stearyl methacrylate, 6.9 g of γ-methacryoxypropyldimethoxymethylsilane, and 55.6 g of IBA was added dropwise over 3.5 hours. Next, a solution of 0.7 g of azobis-2-methylbutyronitrile dissolved in 13.1 g of IBA was added dropwise to the reaction vessel over 1 hour. Polymerization was then carried out after 2 hours to obtain an isobutyl alcohol solution of a (meth)acrylic copolymer (B-1) having dimethoxymethylsilyl groups, with a solid content of 70% by weight, a number average molecular weight of 8,700, and a weight average molecular weight of 18,900.

[0134] [Synthesis Example 3] To 90.3 g of isobutyl alcohol (IBA) heated to 105°C in a reaction vessel, a solution of 1.1 g of azobis-2-methylbutyronitrile dissolved in a mixture of 35.2 g of methyl methacrylate, 193.6 g of butyl acrylate, 45.8 g of 2-ethylhexyl acrylate, 70.4 g of stearyl methacrylate, 3.5 g of γ-methacryoxypropyldimethoxymethylsilane, and 43.9 g of IBA was added dropwise over 3.5 hours. Next, a solution of 0.3 g of azobis-2-methylbutyronitrile dissolved in 15.7 g of IBA was added dropwise to the reaction vessel over 1 hour. Polymerization was then carried out after 2 hours to obtain an isobutyl alcohol solution of a (meth)acrylic polymer (B-2) having dimethoxymethylsilyl groups, with a solid content of 70% by weight, a number average molecular weight of 15,100, and a weight average molecular weight of 41,600.

[0135] [Synthesis Example 4] To 90.9 g of isobutyl alcohol (IBA) heated to 105°C in a reaction vessel, a solution of 1.1 g of azobis-2-methylbutyronitrile dissolved in a mixture of 34.9 g of methyl methacrylate, 191.7 g of butyl acrylate, 45.3 g of 2-ethylhexyl acrylate, 69.7 g of stearyl methacrylate, 7.0 g of γ-methacryoxypropyldimethoxymethylsilane, and 43.5 g of IBA was added dropwise over 3.5 hours. Next, a solution of 0.3 g of azobis-2-methylbutyronitrile dissolved in 15.6 g of IBA was added dropwise to the reaction vessel over 1 hour. Polymerization was then carried out after 2 hours to obtain an isobutyl alcohol solution of a (meth)acrylic polymer (B-3) having dimethoxymethylsilyl groups, with a solid content of 70% by weight, a number average molecular weight of 15,500, and a weight average molecular weight of 43,500.

[0136] [Synthesis Example 5] To 91.5 g of isobutyl alcohol (IBA) heated to 105°C in a reaction vessel, a solution of 1.1 g of azobis-2-methylbutyronitrile dissolved in a mixture of 34.5 g of methyl methacrylate, 189.8 g of butyl acrylate, 44.9 g of 2-ethylhexyl acrylate, 69.0 g of stearyl methacrylate, 10.4 g of γ-methacryoxypropyldimethoxymethylsilane, and 43.1 g of IBA was added dropwise over 3.5 hours. Next, a solution of 0.3 g of azobis-2-methylbutyronitrile dissolved in 15.5 g of IBA was added dropwise to the reaction vessel over 1 hour. Polymerization was then carried out after 2 hours to obtain an isobutyl alcohol solution of a (meth)acrylic polymer (B-4) having dimethoxymethylsilyl groups, with a solid content of 70% by weight, a number average molecular weight of 14,800, and a weight average molecular weight of 41,000.

[0137] [Synthesis Example 6] To 91.5 g of isobutyl alcohol (IBA) heated to 105°C in a reaction vessel, a solution of 1.1 g of azobis-2-methylbutyronitrile dissolved in a mixture of 103.5 g of methyl methacrylate, 131.2 g of butyl acrylate, 34.5 g of 2-ethylhexyl acrylate, 69.0 g of stearyl methacrylate, 10.4 g of γ-methacryoxypropyldimethoxymethylsilane, and 43.1 g of IBA was added dropwise over 3.5 hours. Next, a solution of 0.3 g of azobis-2-methylbutyronitrile dissolved in 15.5 g of IBA was added dropwise to the reaction mixture over 1 hour. Polymerization was then carried out after 2 hours to obtain an isobutyl alcohol solution of a (meth)acrylic polymer (B-5) having dimethoxymethylsilyl groups, with a solid content of 70% by weight, a number average molecular weight of 15,800, and a weight average molecular weight of 39,200.

[0138] (Measurement of the physical properties of cured materials) 4 g (2.8 g solids) of isobutyl alcohol solutions of (meth)acrylic polymers (B-1) to (B-5) obtained in Synthesis Examples 2 to 6 were mixed with 0.056 g of Neostan U-220H (manufactured by Nitto Chemical Co., Ltd.: dibutyltin bisacetylacetonate), and the foam was removed by centrifugation. The resulting mixture was applied to a Teflon sheet with a 10 mil applicator. The formed coating film was cured at room temperature for 30 minutes, then cured at 105°C for 1 hour, 23°C for 3 days, and 50°C for 4 days to obtain a cured sheet. Strip-shaped test pieces with a width of 5 mm were prepared from the obtained sheet, and tensile tests were performed using a Shimadzu Autograph (AGS-J) at a tensile speed of 10 mm / min to determine the breaking strength TB (N / mm²). 2 The saturation, elongation at break (EB), and elongation at break (EB) were measured. The results are shown in Table 1.

[0139] [Table 1]

[0140] [Comparative Example 1] Sixty parts by weight of polyoxypropylene (A-1) obtained in Synthesis Example 1 and an isobutyl alcohol solution containing 40 parts by weight of (meth)acrylic polymer (B-1) obtained in Synthesis Example 2 as solid content were mixed, and then the isobutyl alcohol was heated and defoliated. To the obtained mixture, 160 parts by weight of Shirotsuya CCR (manufactured by Shiraishi Kogyo Co., Ltd.: precipitated calcium carbonate), 54 parts by weight of Whiteon SB (manufactured by Shiraishi Calcium Co., Ltd.: heavy calcium carbonate), 5 parts by weight of Typeque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide), 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisodecyl phthalate), 2 parts by weight of Disparon 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide wax), 1 part by weight of Tinuvin 326 (manufactured by BASF: benzotriazole-based UV absorber), and 1 part by weight of LS770 (manufactured by Ciba Specialty Chemicals: hindered amine-based light stabilizer) were mixed and passed through three paint rolls three times to uniformly disperse. After this, the obtained mixture was dehydrated under reduced pressure at 120°C for 2 hours. After cooling the dehydrated mixture to below 50°C, 3 parts by weight of A-171 (Momentive: vinyltrimethoxysilane) and 3 parts by weight of A-1120 (Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) were added to the mixture and mixed. Then, 2 parts by weight of Neostan U-220H (Nitto Chemical Co., Ltd.: dibutyltin bisacetylacetonate) were added to the mixture and kneaded to obtain a curable composition. The obtained curable composition was sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0141] (Dumbbell tensile properties) The obtained curable composition was filled into a mold and cured for 3 days at 23°C and 50% relative humidity, and then for 4 days at 50°C to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched out into a No. 3 dumbbell shape, and a tensile strength test was performed in an atmosphere of 23°C and 50% relative humidity, and the modulus (M100) at 100% elongation was measured. In addition, the breaking strength TB (MPa) and breaking elongation EB (%) were measured. The measurements were performed using a Shimadzu Autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in Table 2.

[0142] (Weather resistance test) The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 3 days, and then at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 1 mm. The obtained sheet-like cured material was cut into 20 mm x 20 mm pieces to obtain test specimens. The test specimens were subjected to illuminance testing at 125 mW / cm² using a metal weather resistance tester (manufactured by Daipla Wintes Co., Ltd., product name: Daipla Metal Weather CW-R8PL-A). 2 A weathering test was conducted under the conditions of a black panel temperature of 63°C and spraying pure water for 2 minutes every 2 hours. The surface of the hardened material was observed every 70 hours of exposure. Table 2 shows the time at which surface cracks were observed in the test specimens.

[0143] [Comparative Example 2, and Examples 1-3] A curable composition was obtained in the same manner as in Comparative Example 1, except that (meth)acrylic polymer (B-1) was replaced with a (meth)acrylic polymer of the type listed in Table 2. Using the obtained curable composition, a dumbbell tensile strength test and a weather resistance test were performed according to the method described above. The results are shown in Table 2. [Table 2]

[0144] The cured product properties (TB) of (meth)acrylic polymer (B) alone could not be measured. When using the curable compositions of Comparative Examples 1 and 2, which include polymer (B-1) or polymer (B-2), the crack initiation time in the weather resistance evaluation was short, at 280 hours and 350 hours. In contrast, the cured product properties (TB) of (meth)acrylic polymer (B) alone were 0.020 N / mm². 2 When using the curable compositions of Examples 1 to 3, which include polymers (B-1) to (B-3) described above, the crack initiation time in the weathering test was 490 hours or more, and the elongation at break (EB) value was also a high value of 500% or more.

Claims

1. The material comprises a polyoxyalkylene polymer (A) having reactive silicon groups, and a (meth)acrylic polymer (B) having reactive silicon groups. The molecular chain of the (meth)acrylic polymer (B) contains constituent units derived from (meth)acrylic acid ester, The number-average molecular weight Mn of the (meth)acrylic polymer (B), measured by gel permeation chromatography, is 10,000 to 20,000 in terms of polystyrene. The ratio Mw / Mn of the weight-average molecular weight Mw of the (meth)acrylic polymer (B), measured by gel permeation chromatography, to Mn is 1.6 or greater. The glass transition temperature of the (meth)acrylic polymer (B) is 0°C or lower. The tensile strength of the cured product of the (meth)acrylic polymer (B) is 0.020 to 0.300 N / mm². ２ And, The fracture strength is, A mixture is obtained by mixing 100 parts by weight of the (meth)acrylic polymer (B) with 2 parts by weight of dibutyltin diacetylacetonate. The mixture is cured to produce a sheet with a thickness of 0.25 ± 0.05 mm. Cut out strip-shaped test pieces with a width of 5 mm from the aforementioned sheet, and Using the aforementioned test specimen, perform a tensile test at a tensile speed of 10 mm / min. A curable composition measured by a method comprising the following.

2. The aforementioned breaking strength is 0.050 to 0.300 N / mm ２ The curable composition according to claim 1.

3. The aforementioned breaking strength is 0.050 to 0.200 N / mm ２ The curable composition according to claim 1.

4. A cured product of the curable composition according to any one of claims 1 to 3.

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