JP6682227B2 - Curable composition - Google Patents

Description

  The present invention provides a curable composition containing an organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon group capable of forming a siloxane bond (hereinafter, also referred to as “reactive silicon group”). Regarding

It is known that an organic polymer having reactive silicon reacts with moisture or the like even at room temperature and is crosslinked by a siloxane condensation reaction of a reactive silicon group to obtain a rubber-like cured product. Among these organic polymers, the polyoxyalkylene polymer having a reactive silicon group has a relatively low viscosity, and therefore is excellent in workability when preparing or using a blended composition. Further, since the obtained cured product has a good performance balance such as mechanical properties, weather resistance and dynamic durability, it is widely used for applications such as sealing materials, adhesives and paints (Patent Document 1).
A curable composition containing a reactive silicon group-containing organic polymer can be adjusted in workability and various physical properties by blending various components such as a filler and a plasticizer. In order to impart weather resistance and adhesiveness, it is useful to use a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylic acid ester-based polymer in combination (Patent Document 2). ). These are used as high weather resistance sealants and industrial adhesives.
Patent Document 3 discloses that a high-strength cured product can be obtained by combining a reactive silicon group-containing polyoxyalkylene and a (meth) acrylic acid ester-based polymer having a reactive silicon group.

JP-A-52-73998 JP-A-59-122541 WO2009-133811

  It is known that by using a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylic acid ester-based polymer in combination, a cured product having a higher strength than that obtained when used alone is obtained. However, there was room for improvement in terms of further improvement of physical properties. An object of the present invention is to provide a curable composition having excellent mechanical properties.

  The present inventors have completed the following inventions as a result of earnest studies for achieving the above object.

That is, the present invention
(1). Formula ^{_{(1): - SiR 1 a}} X 3-a (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X's each independently represent a hydroxyl group or a hydrolyzable group. A represents 0 or 1.)
A monomer having a reactive silicon group and a polymerizable unsaturated group represented by, and a number average molecular weight of 1,000 having a reactive silicon group and a polymerizable unsaturated group represented by the general formula (1). To 30,000 oxyalkylene macromonomer (a) as a constituent monomer, a (meth) acrylic acid ester-based polymer (A) -containing curable composition,
(2). The curable composition according to (1), wherein the composition contains a polyoxyalkylene polymer (B) having a reactive silicon group,
(3). A sealant composition containing the curable composition according to (1) or (2),
(4). An adhesive composition containing the curable composition according to (1) or (2),
(5). A cured product of the curable composition according to (1) or (2),
Regarding

  The curable composition of the present invention has a low viscosity as compared with the molecular weight and gives a cured product having excellent mechanical properties.

  In the curable composition of the present invention, each of the polymer (A), the polymer (B), and the other components described below may be used alone or in combination of two or more. Good. Hereinafter, each component will be described in order.

<Polymer (A)>
The (meth) acrylic acid ester-based polymer (A) is represented by a monomer having a reactive silicon group and a polymerizable unsaturated group represented by the following general formula (1), and a general formula (1). Is a polymer having, as a constituent monomer, an oxyalkylene macromonomer (a) having a reactive silicon group and a polymerizable unsaturated group and a number average molecular weight of 1,000 to 30,000.
—SiR ¹ _a X _3-a (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X's each independently represent a hydroxyl group or a hydrolyzable group. A represents 0 or 1.)
In the present invention, “(meth) acrylic” means “acrylic and / or methacrylic”.

  The (meth) acrylic acid ester-based polymer (A) of the present invention has a reactive silicon group represented by the general formula (1) at the molecular chain terminal and / or side chain.

Examples of R ¹ in the general formula (1) include an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; ') A triorganosiloxy group represented by ₃ (in the above formula, R's each independently represent an alkyl group (eg, methyl group, etc.) or an aryl group (eg, phenyl group, etc.)); Fluoroalkyl group such as difluoromethyl group; chloroalkyl group such as chloromethyl group, 1-chloroethyl group; alkoxyalkyl group such as methoxymethyl group, ethoxymethyl group, phenoxymethyl group, 1-methoxyethyl group; aminomethyl group, Aminoalkyl groups such as N-methylaminomethyl group and N, N-dimethylaminomethyl group; acetoxymethyl group, methyl Examples thereof include a rucarbamate group and a 2-cyanoethyl group. From the viewpoint of availability of raw materials, R ¹ is preferably a methyl group.

  Examples of the hydrolyzable group represented by X in the general formula (1) include known hydrolyzable groups. Here, the hydrolyzable group means a group that reacts and decomposes in the coexistence of water. Examples of the hydrolyzable group include hydrogen, halogen, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, an amino group, an amido group, an aminooxy group and a mercapto group. Of these, halogen, an alkoxy group (eg, methoxy group, ethoxy group), an alkenyloxy group (eg, isopropenyloxy group (also known as isopropenoxy group)), and an acyloxy group are preferable because of their high activity, and they are hydrolyzable. Is more preferable because it is mild and easy to handle, and a methoxy group and an ethoxy group are particularly preferable. When the hydrolyzable group is an ethoxy group or an isopropenyloxy group, the compound that is eliminated by hydrolysis is ethanol or acetone, respectively. Therefore, from the viewpoint of safety, an ethoxy group and an isopropenyloxy group are preferable as the hydrolyzable group.

  The reactive silicon group represented by the general formula (1) may be one type or two or more types. Specifically, preferably a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, (Chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (ethoxymethyl) dimethoxysilyl group, dimethoxymethylsilyl group is preferred because the reaction is mild and easy to handle, A trimethoxysilyl group is preferable because a composition having a fast curing rate can be obtained.

Examples of the monomer having a reactive silicon group and a polymerizable unsaturated group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acryl. Roxypropyldimethoxymethylsilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyldimethoxymethylsilane and other compounds having a (meth) acryloxy group and a reactive silicon group; vinyltrimethoxysilane, vinyltriethoxysilane Examples thereof include compounds having a vinyl group and a reactive silicon group. These compounds may be used alone or in combination of two or more.
The content of the monomer having a reactive silicon group and a polymerizable unsaturated group in all the monomers constituting the polymer (A) is preferably 0.1 to 90% by weight, and 0.5 to 50% by weight. % Is more preferred, and 1-30% by weight is even more preferred.
The macromonomer (a) constituting the polymer (A) is a polyoxyalkylene having a reactive silicon group and a polymerizable unsaturated group and a number average molecular weight of 1,000 to 30,000.

  Examples of the main chain of the oxyalkylene macromonomer (a) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxy. Butylene copolymers and the like can be mentioned. The main chain of the oxyalkylene macromonomer (a) may be composed of only one type of structural unit or may be composed of two or more types of structural units. In particular, when the curable composition of the present invention is used in a sealant, an adhesive, etc., an oxypropylene containing structural unit of oxypropylene is contained in an amount of 50% by weight or more, preferably 80% by weight or more, based on all the structural units. It is desirable to use the propylene-based macromonomer (a). Such an oxypropylene-based macromonomer (a) is amorphous and has a relatively low viscosity.

  The macromonomer (a) may be linear or branched. The macromonomer (a) is preferably linear, because a cured product having a high elongation can be obtained.

  Polyoxyalkylene can be produced by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator. Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, tetrahydrofuran and the like. These cyclic ether compounds may be used alone or in combination of two or more. Of these cyclic ether compounds, propylene oxide is preferable because it gives amorphous polyoxyalkylene having a relatively low viscosity.

  The initiator is preferably a compound having one hydroxyl group in one molecule, for example, alcohols such as ethanol, propanol, butanol, and allyl alcohol; one hydroxyl group of glycols such as ethylene glycol monoallyl ether is blocked. The compound etc. are mentioned. In order to introduce a reactive silicon group at the terminal, unsaturated alcohol is preferable, and specifically, allyl alcohol and ethylene glycol monoallyl ether are preferable.

  The method for synthesizing polyoxyalkylene is not particularly limited, but examples thereof include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin shown in JP-A-61-215623. Polymerization method using a transition metal compound-porphyrin complex catalyst, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. U.S. Pat. No. 3,427,335, etc., a polymerization method using a complex metal cyanide complex catalyst, a polymerization method using a catalyst composed of a polyphosphazene salt exemplified in JP-A-10-273512, and JP-A-11-060722. Uses a catalyst consisting of a phosphazene compound That polymerization method, and the like. A polymerization method using a complex metal cyanide complex catalyst (for example, zinc hexacyanocobaltate glyme complex catalyst) is preferable for reasons such as production cost and obtaining a polymer having a narrow molecular weight distribution.

  The macromonomer (a) is a polymerizable polymer constituting the polymer (A) and has a polymerizable unsaturated group. The polymerizable unsaturated group may be introduced at either the molecular chain end or the side chain, but it is preferably introduced at the molecular chain end because good elongation properties can be obtained.

  The polymerizable unsaturated group is not particularly limited as long as it is an unsaturated group in which a polymerization reaction proceeds by a general radical polymerization method, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a methallyl group. To be An acryloyl group and a methacryloyl group are preferred because they exhibit good polymerizability.

The method of introducing the polymerizable unsaturated group into the macromonomer (a) is not particularly limited, and for example, the methods shown in the following (i) to (ii) can be used.
(I) A compound having a polyoxyalkylene (hereinafter, also referred to as “precursor polymer”) as a raw material, a functional group capable of reacting with a hydroxyl group (eg, isocyanate) and a polymerizable unsaturated group (eg, methacryloyloxy). Ethyl isocyanate and acryloyloxyethyl isocyanate) and the like.
(Ii) A method of reacting a carboxylic acid chloride (eg, methacryloyl chloride, acryloyl chloride, etc.) after alkoxidizing the hydroxyl groups of the precursor polymer.

  The method (i) is preferable because the reaction is simple, and the method (ii) is economically preferable.

The macromonomer (a) has a reactive silicon group. The reactive silicon group is represented by the general formula (1) and may be one type or two or more types. As the reactive silicon group represented by the general formula (1), those specifically exemplified above can be used, and a dimethoxymethylsilyl group or trimethoxysilyl group can be obtained because a cured product having excellent tensile properties can be obtained. Groups are preferred.
The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. For example, a method of adding a hydrosilane compound to an unsaturated bond by a hydrosilylation reaction can be mentioned.
Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, and (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, triethoxysilane, and (chloromethyl). ) Alkoxysilanes such as dimethoxysilane and (methoxymethyl) dimethoxysilane; and isopropenyloxysilanes such as triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, and (methoxymethyl) diisopropenyloxysilane. Can be mentioned.

  The macromonomer (a) has an average of more than 0.4, preferably 0.5 or more, reactive silicon groups represented by the general formula (1) in one molecule. The upper limit of the number (average value) of reactive silicon groups in one molecule of the macromonomer (a) is preferably 1.0.

In the present invention, the number of reactive silicon groups (average value) in one molecule of the macromonomer (a) is the average value of the protons on the carbon to which the reactive silicon groups are directly bonded, measured and calculated by the high resolution ¹ H-NMR method. It is defined as In the measurement and calculation of the number of reactive silicon groups, when the reactive silicon group was introduced into the precursor polymer, the precursor polymer in which the reactive silicon group was not introduced and the reactive silicon group obtained by the side reaction were introduced. A polymer that does not exist is regarded as a part of the macromonomer (a) and is included in the population parameter (the number of molecules of the macromonomer (a)) when the number of reactive silicon groups (average value) is calculated.

  The number average molecular weight of the macromonomer (a) is 1,000 or more, more preferably 3,000 or more, particularly preferably 5,000 or more, and the upper limit is 30,000 or less, more preferably 15,000 or less. is there. When the number average molecular weight of the macromonomer (a) is small, the viscosity of the polymer (A) is low, but good tensile physical properties tend not to be obtained. On the other hand, when the number average molecular weight of the macromonomer (a) is large, the elongation of the cured product is improved, but when it is too large, the viscosity tends to be too high and the handling tends to be difficult.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the macromonomer (a) is not particularly limited, but is preferably narrow, less than 2.0 is more preferable, 1.6 or less is further preferable, Particularly preferred is 1.5 or less, and most preferred is 1.4 or less.

  The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the macromonomer (a) are values measured by GPC (in terms of polystyrene), and detailed measuring methods are described in Synthesis Example 1 described later. The same is true for measuring the number average molecular weight (Mn) of other components (polymer (A), polymer (B), high molecular weight plasticizer, etc.).

The macromonomer of the polymer (A) may be introduced at either the terminal of the molecular chain or the side chain, but is preferably introduced at the side chain from the viewpoint of adhesiveness. The number of macromonomers in one molecule of the polymer (A) is, on average, preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, preferably 2.0 or less, It is more preferably 1.5 or less, still more preferably 1.3 or less.
The content of the macromonomer (a) in all the monomers constituting the polymer (A) is preferably 1 to 90% by weight, more preferably 5 to 70% by weight, still more preferably 10 to 50% by weight. .

The (meth) acrylic acid ester-based monomer that constitutes the main chain structure of the (meth) acrylic acid ester-based polymer (A) is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Acid phenyl, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methacrylate (meth) acrylate Xyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, (meth) acrylic acid 2,2 , 2-trifluoroethyl, (meth) acrylic acid 3,3,3-trifluoropropyl, (meth) acrylic acid 3,3,4,4,4-pentafluorobutyl, (meth) acrylic acid 2-perfluoro Ethyl-2-perfluorobutylethyl, (meth) acrylic acid trifluoromethyl, (meth) acrylic acid perfluoroethyl, (meth) acrylic acid bis (trifluoromethyl) methyl, (meth) acrylic acid 2-trifluoromethyl -2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, (meth ) 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate and the like can be mentioned.
The content of the (meth) acrylic acid ester-based monomer in all monomers constituting the polymer (A) is preferably 10 to 99% by weight, more preferably 30 to 95% by weight, and 50 to 90% by weight. Are even more preferred.
You may use the other monomer which shows a copolymerizability with the said monomer. Examples of the other monomer include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyl such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Monomers: Maleic acid, maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and other maleic acid and its derivatives; Fumaric acid, fumaric acid monoalkyl ester, fumaric acid dialkyl ester and other fumaric acid and its derivatives; Maleimide simple substances such as maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide. Body; vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; olefinic monomers such as ethylene and propylene; conjugated diene-based monomers such as butadiene and isoprene Body; (meth) acrylamide; (meth) acrylonitrile; vinyl-based monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. The other monomers may be used alone or in combination of two or more.
The content of the above-mentioned other monomers in the total monomers constituting the polymer (A) is preferably 1 to 80% by weight, more preferably 5 to 60% by weight, and further preferably 5 to 40% by weight. More preferable.

  The polymer (A) can be obtained by various polymerization methods, and the polymerization method is not particularly limited, but the radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of control.

  The radical polymerization method can be classified into "general radical polymerization method" and "controlled radical polymerization method". The "general radical polymerization method" is a simple polymerization method which is a method of simply polymerizing using a polymerization initiator such as an azo compound or a peroxide. On the other hand, the "controlled radical polymerization method" is a method capable of introducing a specific functional group at a controlled position such as a terminal. The “controlled radical polymerization method” can be further classified into a “chain transfer agent method” and a “living radical polymerization method”. The "chain transfer agent method" is characterized in that polymerization is carried out using a chain transfer agent having a specific functional group, and a vinyl polymer having a functional group at the terminal is obtained. On the other hand, the "living radical polymerization method" is characterized in that the polymer growing terminal grows without causing side reactions such as termination reaction, and a polymer having a molecular weight almost as designed is obtained. In the present invention, any of these polymerization methods may be used.

  Specific examples of the “general radical polymerization method” include a solution polymerization method and a bulk polymerization method in which a polymerization initiator, a chain transfer agent, a solvent and the like are added and polymerization is performed at 50 to 150 ° C.

  Examples of the polymerization initiator include 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and 2,2′-azobis (2,4-). Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 1,1 Azo compounds such as'-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, isobutyryl peroxide, isonanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3 , 5,5-Trimethylhexanoyl) peroxide, etc .; diacyl peroxide; Peroxydicarbonate, di-sec-butylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-1-methylheptylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, dicyclohexylperoxy Peroxydicarbonates such as dicarbonates; tert-butylperoxybenzoate, tert-butylperoxyacetate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxypyroxy. Peroxyesters such as barrate, tert-butyldiperoxyadipate, cumylperoxyneodecanoate; keto such as methyl ethyl ketone peroxide, cyclohexanone peroxide Peroxide; Dialkyl peroxide such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane; Hydroperoxides such as cumene hydroxyperoxide and tert-butyl hydroperoxide; peroxides such as 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the chain transfer agent include mercapto group-containing compounds such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan. Moreover, when introducing a reactive silicon group into the molecular chain terminal of the (meth) acrylic polymer, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxy. It is preferable to use a compound having a reactive silicon group and a mercapto group, such as silane, 3-mercaptopropylmethoxymethyldimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, (mercaptomethyl) trimethoxysilane. These may use only 1 type and may use 2 or more types together. When it is desired to obtain a cured product having excellent weather resistance, it is preferable not to use the mercapto group-containing compound during the polymerization.

  Examples of the solvent include aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate and di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane and the like. Hydrocarbon compounds; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate Compounds: alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, amyl alcohol and the like can be mentioned. Among these, one or more selected from dialkyl carbonate compounds and alcohol compounds are preferable from the viewpoint of odor, environmental load and the like. Furthermore, the boiling point is measured according to the GEV (Gemain shaft emission control reel Teferigewergstoffee AVE) GEV Specification and Classification Criteria February 14, 2001 edition. From the viewpoint of suppressing the emission of all volatile organic compounds from the composition, dimethyl carbonate, n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol. Is more preferable, and 2-propanol and isobutanol are even more preferable.

  In the synthesis of the polymer (A), it is also possible to polymerize the monomer of the polymer (A) together with the polymer (B) and its precursor compound, the plasticizer described later and the like.

  The “chain transfer agent method” is a polymerization method capable of quantitatively introducing a functional group at the polymer terminal, as compared with the “general radical polymerization method”. The radical polymerization using a chain transfer agent is not particularly limited, but for example, a halogen-terminated polymer is obtained by using a halogenated hydrocarbon as disclosed in JP-A-4-132706 as a chain transfer agent. Method, hydroxyl group-containing mercaptan or hydroxyl group-containing polysulfide as disclosed in JP-A-61-271306, JP-A-2594402 and JP-A-54-47782 is used as a chain transfer agent, and the weight of the hydroxyl group end is increased. Examples include a method of obtaining a coalescence.

The "living radical polymerization method" is different from the above-mentioned polymerization method, in which a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained, and a monomer having a specific functional group is added. It is a polymerization method that can be introduced into almost any position of a polymer. In the narrow sense, living polymerization refers to polymerization in which the terminal always keeps active and the molecular chain grows, but generally, the terminal is inactivated and activated. It also includes pseudo-living polymerization that grows in equilibrium.
The "living radical polymerization method" uses, for example, a cobalt porphyrin complex as shown in Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943. In particular, those using a nitroxide radical as disclosed in JP-A-2003-500378, an organic halide or a sulfonyl halide compound as disclosed in JP-A No. 11-130931 as an initiator. , Atom Transfer Radical Polymerization (ATRP method) using a transition metal complex as a catalyst. Further, in the present invention, so-called reverse atom transfer radical polymerization, that is, a normal atom transfer radical polymerization catalyst, as shown in Macromolecules, 1999, Volume 32, page 2872, produces radicals. A general radical initiator such as a peroxide is caused to act on Cu (II) when a high oxidation state (for example, Cu (I) is used as a catalyst) when it is generated, and as a result, an atom transfer radical is generated. A polymerization method that produces an equilibrium state similar to polymerization is also included in the atom transfer radical polymerization method.

  As a polymerization method other than these, an acrylic polymer is prepared by using a metallocene catalyst as disclosed in JP 2001-040037 A and a thiol compound having at least one reactive silicon group in the molecule. A method of obtaining the same or a vinyl monomer as described in JP-A-57-502171, JP-A-59-006207 and JP-A-60-511992 is used in a stirred tank reactor. It is also possible to use a high temperature continuous polymerization method in which the continuous polymerization is performed.

The method for introducing the reactive silicon group into the (meth) acrylic acid ester-based polymer is not particularly limited, and for example, the following methods (I) to (IV) can be used.
(I) A method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group with a (meth) acrylic acid ester.
(II) A method of copolymerizing a (meth) acrylic acid ester in the presence of the above-mentioned compound having a reactive silicon group and a mercapto group as a chain transfer agent.
(III) Copolymerization of a compound having a polymerizable unsaturated bond and a reactive functional group (Z group) (for example, acrylic acid or 2-hydroxyethyl acrylate) with a (meth) acrylic acid ester having no Z group. And then reacting a compound having a functional group that reacts with the reactive silicon group and the Z group (for example, an isocyanate silane compound).
(IV) A method in which a (meth) acrylic acid ester is polymerized by a living radical polymerization method and then a reactive silicon group is introduced at the terminal of the molecular chain.

In addition, you may use these methods arbitrarily combining.
It is preferable to use a combination of the above methods (I) and (II) from the viewpoint that a reactive silicon group can be introduced into both the molecular chain terminal and the side chain. Further, the method (IV) is preferable because a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained.

  Examples of the compound having a reactive silicon group and a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, mercaptomethyltrimethoxysilane, mercaptomethyldimethoxymethylsilane, and 3-mercaptopropyltriethoxysilane. , Mercaptomethyltriethoxysilane and the like. Examples of the compound having a polymerizable unsaturated bond and a reactive silicon group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and (meth) acryloxymethyltrimethoxysilane. Compounds having a (meth) acryloxy group and a reactive silicon group such as silane, (meth) acryloxymethyldimethoxymethylsilane, 3- (meth) acryloxypropyldimethoxymethylsilane, and (meth) acryloxymethyldimethoxymethylsilane; vinyl; Examples thereof include compounds having a vinyl group and a reactive silicon group such as trimethoxysilane and vinyltriethoxysilane. These may be used alone or in combination of two or more.

The reactive silicon group of the polymer (A) may be introduced at either the molecular chain terminal or the side chain, but from the viewpoint of adhesiveness, it is preferably introduced at both the molecular chain terminal and the side chain. . On average, the number of reactive silicon groups in one molecule of the polymer (A) is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, and preferably 8. It is 0 or less, more preferably 7.0 or less, and further preferably 6.0 or less.
The molecular weight of the polymer (A) is not particularly limited. In order to obtain a cured product having higher strength, it is preferable that the polymer (A) has a high molecular weight. The number average molecular weight is, in terms of polystyrene by GPC, preferably 2,000 or more, more preferably 3,000 or more, further preferably 4,000 or more, preferably 100,000 or less, more preferably 50,000 or less. , And more preferably 30,000 or less.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A) is not particularly limited, but is preferably less than 4.0, particularly preferably 3.0 or less.

  When the polymer (A) is used as a mixture with the polymer (B), from the viewpoint of compatibility with the polymer (B), a structural unit derived from the alkyl (meth) acrylate of the polymer (A) is used. The amount is preferably 50% by weight or more, more preferably 70% by weight or more, preferably 98% by weight or less, more preferably 95% by weight or less, based on the total constitutional units.

  In order to improve the compatibility with the polymer (B), the monomer constituting the polymer (A) is an alkyl (meth) acrylate in which the alkyl has 1 to 6 carbon atoms (hereinafter referred to as “monomer”). (Also referred to as “(b)”), and an alkyl (meth) acrylate (hereinafter, referred to as “monomer (c)”) having 7 to 30 carbon atoms. That is, the polymer (A) includes a structural unit derived from the monomer (b) (hereinafter also referred to as “structural unit (b)”) and a structural unit derived from the monomer (c) (hereinafter “structural unit”). (Also referred to as “(c)”). The total amount of the monomer (b) and the monomer (c) in all the monomers constituting the polymer (A) (that is, the structural unit (b) in all the structural units of the polymer (A) and The total amount of the structural unit (c)) is preferably 50 to 95% by weight, more preferably 60 to 90% by weight. Further, the weight ratio of the monomer (b) and the monomer (c) (monomer (b) :( c)), that is, the weight ratio of the structural unit (b) and the structural unit (c) (the structural unit (B): The structural unit (c)) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40.

<Polymer (B)>
The curable composition of the present invention may contain an oxyalkylene polymer (B).

The oxyalkylene polymer (B) has the following general formula (2):
^{_{-SiR 1 a X 3-a (}} 2)
(In the formula, R ¹ and X are the same as those in the general formula (1). A represents 0 or 1.)
It has a reactive silicon group represented by.

  The reactive silicon group represented by the general formula (2) may be one type or two or more types. The reactive silicon group represented by the general formula (2) is preferably one kind, more preferably a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, dimethoxy. Methylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, or (ethoxymethyl) dimethoxysilyl group And a dimethoxymethylsilyl group or a trimethoxysilyl group is preferable because a cured product having high adhesive strength can be obtained.

  Examples of the main chain of the oxyalkylene polymer (B) (that is, the polyoxyalkylene portion having no reactive silicon group) include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, and polyoxyethylene. Examples thereof include oxyethylene-polyoxypropylene copolymers and polyoxypropylene-polyoxybutylene copolymers. The main chain of the oxyalkylene polymer (B) may be composed of only one type of structural unit or may be composed of two or more types of structural units. In particular, when the curable composition of the present invention is used in a sealant, an adhesive, etc., an oxypropylene containing structural unit of oxypropylene is contained in an amount of 50% by weight or more, preferably 80% by weight or more, based on all the structural units. It is desirable to use the propylene polymer (B). Such an oxypropylene polymer (B) is amorphous and has a relatively low viscosity.

  The polymer (B) may be linear or branched. The polymer (A) is preferably linear, since a cured product having a high elongation can be obtained. When the polymer (A) is branched, the number of branched chains is preferably 1 to 4, more preferably 1.

  The polyoxyalkylene containing no reactive silicon group can be produced by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator. Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, tetrahydrofuran and the like. These cyclic ether compounds may be used alone or in combination of two or more. Of these cyclic ether compounds, propylene oxide is preferable because it gives amorphous polyoxyalkylene having a relatively low viscosity.

  Examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol and sorbitol. Alcohols; hydroxyl group-containing polyoxyalkylenes having a number average molecular weight of 300 to 4,000 such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol and polyoxyethylene triol.

  The method for synthesizing the polyoxyalkylene containing no reactive silicon group is not particularly limited, but, for example, a polymerization method using an alkali catalyst such as KOH, a reaction between an organoaluminum compound disclosed in JP-A-61-215623 and a porphyrin is performed. Polymerization method using a transition metal compound-porphyrin complex catalyst such as a complex thus obtained, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Patent 3427256, U.S. Pat. No. 3,427,334, U.S. Pat. No. 3,427,335, and the like. No. 060722 Polymerization method using a catalyst comprising a down compounds. A polymerization method using a complex metal cyanide complex catalyst (for example, zinc hexacyanocobaltate glyme complex catalyst) is preferable for reasons such as production cost and obtaining a polymer having a narrow molecular weight distribution.

  The method for introducing a reactive silicon group into polyoxyalkylene is not particularly limited, and a known method can be used. Examples of the method of introducing a reactive silicon group include the following methods (i) and (ii).

(I) Hydrosilylation A method may be mentioned in which an unsaturated bond is introduced into a polyoxyalkylene (hereinafter, also referred to as “precursor polymer”) as a raw material and a hydrosilane compound is added to the unsaturated bond by a hydrosilylation reaction. There is no particular limitation on the method of introducing the unsaturated bond, for example, a precursor polymer having a functional group such as a hydroxyl group is reacted with a compound having a group and an unsaturated bond to react with the functional group to form a bond, A method of obtaining a polymer having an unsaturated bond; a method of polymerizing a monomer having an unsaturated bond; and the like.

  Examples of the hydrosilane compound that can be used in the method (i) include halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, and (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, and trimethoxy. Alkoxysilanes such as silane, triethoxysilane, (chloromethyl) dimethoxysilane, (methoxymethyl) dimethoxysilane; triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane And other isopropenyloxysilanes.

(Ii) Reaction of Reactive Group-Containing Polymer (Precursor Polymer) with Silane Coupling Agent A precursor polymer having a functional group such as a hydroxyl group, an amino group, and an unsaturated bond is reacted with the functional group to form a bond. Examples thereof include a method of reacting with a compound (silane coupling agent) having both a group to be formed (hereinafter also referred to as “reactive group”) and a reactive silicon group. As the combination of the functional group of the precursor polymer and the reactive group of the silane coupling agent, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, amino Examples thereof include, but are not limited to, a group and an α, β-unsaturated carbonyl group (reaction by Michael addition), a carboxy group and an epoxy group, an unsaturated bond and a mercapto group, and the like.

  Examples of the silane coupling agent that can be used in the method (ii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, and mercapto that react with an unsaturated bond. Mercaptosilanes such as methyltriethoxysilane and mercaptomethyldimethoxymethylsilane; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, and isocyanatemethyltrimethoxysilane that react with hydroxyl groups , Isocyanate methyltriethoxysilane, isocyanate methyldimethoxymethylsilane and other isocyanate silanes; hydroxyl group, amino group or carboxy group 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycid Epoxysilanes such as xymethyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3- (2- Aminoethyl) propyltrimethoxysilane, 3- (2-aminoethyl) propyldimethoxymethylsilane, 3- (2-aminoethyl) propyltriethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimetho Sisilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane , N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, Examples thereof include aminosilanes such as bis (3- (trimethoxysilyl) propyl) amine; hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane.

  The method (i) has the advantages that the reaction is simple, the amount of the reactive silicon group introduced can be adjusted, and the physical properties of the resulting reactive silicon group-containing polymer (B) are stable. Have. The above method (ii) has many reaction options and has an advantage that it is easy to increase the reactive silicon group introduction rate. The reactive silicon group may be introduced into the polyoxyalkylene by a known method other than the above (i) and (ii).

The main chain of the polymer (B) has an ester bond or a general formula (3):
^{-NR 2 -C (= O) -} (3)
(In the formula, R ² represents an organic group having 1 to 10 carbon atoms or a hydrogen atom) and may include an amide segment.

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

  Examples of the amide segment represented by the general formula (3) include a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, a reaction between an isocyanate group and a mercapto group, and the like. The thing formed by this can be mentioned. Further, those formed by the reaction of the amide segment containing an active hydrogen atom and an isocyanate group are also included in the amide segment represented by the general formula (3).

As a method for producing the polymer (B) containing an amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to give a polymer having an isocyanate group at the terminal. After the synthesis or at the same time as the synthesis, the general formula (4):
_{^{Z-R 3 -SiR 1 a X}} 3-a (4)
(In the formula, R ¹ , X and a are the same as above. R ³ is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group, It is a carboxy group, a mercapto group, a primary amino group or a secondary amino group.)
A method of reacting the Z group of the silicon compound represented by with all or a part of the isocyanate groups of the synthesized polymer can be mentioned.

  The silicon compound represented by the general formula (4) is not particularly limited, but for example, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrisilane. Amino group-containing silanes such as methoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxymethylsilane, (N-phenyl) -γ-aminopropyltrimethoxysilane and N-ethylaminoisobutyltrimethoxysilane; Hydroxyl group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; and the like. Further, JP-A-6-212879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,756,751), JP-A-10-204144 (EP0831108), JP-A-2000-169544, and JP-A-2000-169545. As described in No. 3, various α, β-unsaturated carbonyl compounds and Michael addition reaction products of primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds The Michael addition reaction product of can also be used as the silicon compound represented by the general formula (4).

In addition, as a method for producing the polymer (B) containing an amide segment, for example, polyoxyalkylene having an active hydrogen-containing group at the terminal can be prepared by adding the compound of the general formula (5):
^{O = C = N-R 3} -SiR 1 a X 3-a (5)
(In the formula, R ³ , R ¹ , X and a are the same as above.)
The method of reacting the reactive silicon group-containing isocyanate compound represented by

  The reactive silicon group-containing isocyanate compound represented by the general formula (5) is not particularly limited, but for example, γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ -Methyldiethoxysilylpropyl isocyanate, γ- (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl) dimethoxy Examples include silyl methyl isocyanate.

  When the polymer (B) contains an amide segment, the number (average value) of amide segments per molecule of the polymer (B) is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 3. Particularly preferred. If this number is less than 1, the curability may not be sufficient, while if it is greater than 10, the polymer (B) may have a high viscosity and may be difficult to handle. In order to reduce the viscosity of the curable composition and improve workability, the polymer (B) preferably contains no amide segment.

  The average number of the polymer (B) in one molecule is more than 1, preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.5 or more, in the general formula (2). ) Has a reactive silicon group. The upper limit of the number of reactive silicon groups (average value) in one molecule of the polymer (B) is preferably 6.0, more preferably 5.5, and further preferably 5.0. If the number of reactive silicon groups is 1 or less, a cured product with high strength may not be obtained, and if the number of reactive silicon groups exceeds 6.0, a cured product with high elongation may not be obtained. is there.

In the present invention, the number of reactive silicon groups (average value) in one molecule of the polymer (B) is an average value obtained by measuring and calculating the protons on carbon to which the reactive silicon groups are directly bonded by a high resolution ¹ H-NMR method. It is defined as In the measurement and calculation of the number of reactive silicon groups, when the reactive silicon group was introduced into the precursor polymer, the precursor polymer in which the reactive silicon group was not introduced and the reactive silicon group obtained by the side reaction were introduced. A polymer that does not exist is regarded as a part of the polymer (B) and is included in the parameter (the number of molecules of the polymer (B)) when calculating the number of reactive silicon groups (average value).

The polymer (B) may have an average of more than one reactive silicon group at one terminal site. Examples of the method for producing the polymer (B) having an average of more than one reactive silicon group at one terminal site include:
(A) reacting a polyoxyalkylene (precursor polymer) having a hydroxyl group at the terminal with an epoxy compound having an unsaturated bond to introduce an unsaturated bond and a hydroxyl group at the terminal of the precursor polymer,
(B) A compound having an unsaturated bond and a group that reacts with a hydroxyl group to form a bond (for example, a halogen atom) is reacted with the obtained polymer to introduce a plurality of unsaturated bonds at the terminal of the polymer. ,
(C) A method of adding a hydrosilane compound to a plurality of unsaturated bonds by a hydrosilylation reaction can be mentioned.

  Examples of the epoxy compound used in the above reaction (a) include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, butadiene monooxide, 1,4-cyclopentadiene monoepoxide, and the like, from the viewpoint of reactivity. Allyl glycidyl ether is preferred. In addition, in this invention, "(meth) allyl" represents "allyl and / or methallyl", and "(meth) acrylate" represents "acrylate and / or methacrylate".

  The amount of the epoxy compound used in the reaction (a) can be appropriately set in consideration of the amount of the unsaturated bond introduced into the polyoxyalkylene (precursor polymer) having a hydroxyl group at the terminal and the reactivity. The amount used is preferably 0.2 mol or more, more preferably 0.5 mol or more, preferably 5.0 mol or less, more preferably 2.0 mol, based on 1 mol of the hydroxyl group in the polyoxyalkylene. It is less than or equal to mol.

  The reaction temperature in the above reaction (a) is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 140 ° C. or lower. If the reaction temperature is low, the reaction hardly proceeds, and if the reaction temperature is too high, the main chain of polyoxyalkylene may be decomposed.

Examples of the compound used in the reaction (b) having a group that reacts with a hydroxyl group to form a bond and an unsaturated bond include 3-chloro-1-propene and 3-chloro-2-methyl-1-propene. Etc. The amount of the compound used in the reaction (b) is preferably 1.1 mol or more, more preferably 1.2 mol or more, and preferably 1.4 mol, based on 1 mol of the hydroxyl group in the polymer. It is below, more preferably below mol.
The end of the polymer obtained by the above reaction (b) has the general formula (6):

(In the formula, R ⁵ and R ⁷ are each independently a divalent organic group having 1 to 10 carbon atoms and optionally containing an oxygen atom or a nitrogen atom. R ⁶ and R ⁸ are each independently. Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.)
It is represented by.

  Examples of the hydrosilane compound used in the reaction (c) include those exemplified in the method (i). The amount of the hydrosilane compound used in the above reaction (c) is preferably 0.65 mol or more, more preferably 0.75 mol or more, and preferably 1. mol per 1 mol of the unsaturated bond in the polymer. It is 1 mol or less, more preferably 1.2 mol or less.

  The number of reactive silicon groups in the polymer (B) is preferably 0.5 or more, more preferably 1.0 or more, and 1.1 or more on average at one terminal site. It is more preferable that the number is 1.5 or more, and the most preferable number is 1.5 or more.

  The number average molecular weight of the polymer (B) is preferably 8,000 or more, more preferably 9,000 or more, even more preferably 10,000 or more, particularly preferably 15,000 or more, most preferably 20,000 or more. And preferably 50,000 or less, more preferably 35,000 or less, and further preferably 30,000 or less. When the number average molecular weight of the polymer (B) is low, its viscosity is low, so that workability when using the curable composition is improved, but the obtained cured product tends to be hard and the elongation tends to be lowered. On the other hand, if the number average molecular weight of the polymer (B) is too large, the reactive silicon group concentration may be too low, and the curing speed may be slow, and the viscosity thereof will be too high, making handling difficult. Tend.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (B) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, Particularly preferred is 1.5 or less, and most preferred is 1.4 or less.

  The weight ratio of the polymer (A) and the polymer (B) is not particularly limited, but the ratio of the polymer (B): polymer (A) is preferably 95: 5 to 30:70, and 85:15. The ratio is more preferably 40:60, further preferably 80:20 to 50:50. Further, the total content of the polymer (A) and the polymer (B) in the curable composition is preferably 10 to 90% by weight, more preferably 30 to 80% by weight.

<Other ingredients>
The curable composition of the present invention may contain components (other components) other than the above-mentioned polymer (A) and polymer (B) as long as the effects of the present invention are not impaired. The other components will be described below.

In the present invention, a curing catalyst is used for the purpose of curing the polymers (A) and (B). Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxy titanium, and diisopropoxy titanium bis (ethyl acetoacetate); Dimethyltin diacetate, dimethyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methyl maleate) , Dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis (benzyl maleate) Dibutyltin diacetate, dioctyltin bis (triethoxysilicate), dioctyltin bis (ethyl maleate), dioctyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyl Tin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, dioctyltin dilaurate, dioctyl Tetravalent organic tin compounds such as tin diacetate and dioctyltin bis (acetylacetonate); aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxy Organoaluminum compounds such as aluminum ethyl acetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); carboxylic acids such as 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid and naphthenic acid; tin carboxylate Lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, carboxylic acid Carboxylic acid metal salts such as nickel and cerium carboxylic acid; 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-to Riazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1,8-diazabicyclo [5.4. 0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and other amidine compounds; boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride ethylamine Boron trifluoride complex such as complex; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3,3,3-hexafluoro-1-diethylamino propane (MEC81, aka Ishikawa reagent), potassium _{hexafluorophosphate, Na 2 SiF 6, K 2} SiF 6, fluorine anion containing such (NH _{4) 2} SiF ₆ And the like can be mentioned compounds, but are not limited to.

  Among these, dibutyltin compounds, dioctyltin compounds, tin carboxylates, and carboxylic acids are preferable because they give a cured product having high strength and high elongation. Dioctyltin compounds, tin carboxylates and carboxylic acids are more preferred because of their low toxicity.

  The amount of the condensation catalyst used is preferably about 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer (A) and the polymer (B). In recent years, there has been a tendency to limit the amount of tin compounds used due to increasing environmental problems. Therefore, when using a tin compound, it is preferably less than 1 part by weight.

  A plasticizer may be added to the curable composition of the present invention. By adding a plasticizer, the viscosity of the curable composition, slump property, and mechanical properties such as hardness, tensile strength, and elongation of a cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butylbenzyl phthalate, and other phthalate ester compounds; bis (2-ethylhexyl) ) -1,4-Benzenedicarboxylate and other terephthalic acid ester compounds (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalic acid ester compounds ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributyl acetylcitrate. And aliphatic polycarboxylic acid ester compounds such as oleic acid; butyl oleate, methyl acetylricinoleate and other unsaturated fatty acid ester compounds; alkylsulfonic acid phenyl ester (specifically, product name: Mesamoll (manufactured by LANXESS)); Phosphoric acid ester compounds such as cresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, benzyl epoxystearate An epoxy plasticizer such as can be mentioned.

  Polymeric plasticizers can also be used. The use of the high-molecular plasticizer can maintain the initial physical properties for a long period of time, as compared with the case of using the low-molecular plasticizer. Further, the drying property (paintability) when the alkyd paint is applied to the cured product can be improved. In order to obtain a cured product having higher strength, it is preferable to use a polymer plasticizer rather than a low molecular weight plasticizer. Specific examples of the polymer plasticizer include (meth) acrylic acid ester-based polymers obtained by polymerizing (meth) acrylic acid ester monomers by various methods; diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester. Polyalkylene glycol esters such as; polyesters 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 -Based plasticizers; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol having a number average molecular weight of 500 or more, and even 1,000 or more; Polyether in which hydroxyl group of ether polyol is urethanized (for example, trade name: LBU-25 (manufactured by Sanyo Kasei Co., Ltd.)), polyether esterified with carboxylic acid, end etherified polyether; polystyrene or poly Polystyrenes such as -α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like can be mentioned, but not limited thereto.

  Among these polymer plasticizers, those compatible with the polymers (A) and (B) are preferable. From this point, a polyether polymer or a (meth) acrylic acid ester polymer is preferable. Further, when a polyether polymer is used as a plasticizer, the surface curability and the deep curability are improved, and curing delay after storage does not occur, which is preferable, and polypropylene glycol is more preferable. It is preferable to use a polyether derivative that does not have a hydroxyl group at the terminal because it can suppress the strength reduction due to the addition of a plasticizer. A (meth) acrylic acid ester-based polymer is preferable because it does not lower the adhesive strength. Among the (meth) acrylic acid ester-based polymers, poly (meth) acrylic acid alkyl ester-based polymers are particularly preferable. As a method for synthesizing this polymer, a living radical polymerization method is preferable, and an atom transfer radical polymerization method is more preferable, because the molecular weight distribution is narrow and the viscosity can be lowered. Further, it is preferable to use a polymer obtained by so-called SGO process, which is obtained by continuous bulk polymerization of (meth) acrylic acid alkyl ester-based monomer described in JP 2001-207157 A at high temperature and high pressure.

  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, and even more preferably 1,000 to 5, in terms of polystyrene equivalent by GPC. 000 is most preferred. The most preferable range is 1,000 to 3,000. If the molecular weight is too low, heat or rainfall causes the plasticizer to flow out over time, making it impossible to maintain the initial physical properties for a long time. Further, if the molecular weight is too high, the viscosity becomes high and the workability becomes poor.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but it is preferably narrow and preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is still more preferable, 1.50 or less is further preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  A polymer plasticizer having a reactive silicon group may be used. Examples of the reactive silicon group include silicon groups represented by the general formula (1). The reactive silicon group can be introduced by the method exemplified for the polymer (A) or the polymer (B). The average lower limit of the number of reactive silicon groups per molecule is preferably 0.3 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more. The upper limit is preferably 1.3 or less. When the number of reactive silicon groups is 0.3 or less, a cured product having high strength may not be obtained, which is not preferable. If the number of reactive silicon groups exceeds 1.3, a cured product with high elongation may not be obtained, which is not preferable.

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B). . If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. The plasticizers may be used alone or in combination of two or more. A low molecular weight plasticizer and a high molecular weight plasticizer may be used in combination. It should be noted that these plasticizers can be added at the time of polymer production. When it is desired that the present curable composition exhibit high strength, it is desirable not to use a plasticizer.

  A solvent or diluent can be added to the composition of the present invention. The solvent and the diluent are not particularly limited, and aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether and the like can be used. When a solvent or a diluent is used, 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, because of the problem of air pollution when the composition is used indoors. . The above solvents or diluents may be used alone or in combination of two or more.

In the curable composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion imparting agent.
Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and α-isocyanatomethyltrimethoxysilane. Isocyanate group-containing silanes such as α-isocyanatomethyldimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N -Β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyi Triethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane Silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylaminomethyl) trimethoxysilane, bis Amino group-containing silanes such as (3-trimethoxysilylpropyl) amine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopro Mercapto group-containing silanes such as trimethylmethylethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4- Epoxy group-containing silanes such as epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) Carboxysilanes such as silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; methyl (N- Carbamate silanes such as dimethoxymethylsilylmethyl) carbamate, methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate; (methoxymethyl) dimethoxy Alkoxy group-containing silanes such as methylsilane, (methoxymethyl) trimethoxysilane, (ethoxymethyl) trimethoxysilane, and (phenoxymethyl) trimethoxysilane; 3- (trimethoxysilyl) propyl Pills succinic anhydride, 3-may be mentioned acid anhydride-containing silanes such as (triethoxysilyl) propyl succinic anhydride and the like. In addition, these partial condensates and their modified derivatives 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 cups. It can be used as a ring agent. These silane coupling agents may be used alone or in combination. As the reaction product of the silane coupling agent, a reaction product of an isocyanate silane with a hydroxyl group-containing compound and an amino group-containing compound; a Michael addition reaction product of aminosilane; a reaction product of an aminosilane and an epoxy group-containing compound, an epoxysilane and a carboxylic acid group Examples thereof also include a compound containing the compound and a reaction product with the compound containing an amino group.

  The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, and particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymers (A) and (B).

  Specific examples of the adhesiveness-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate, and the like. The above-mentioned adhesiveness imparting agents may be used alone or in combination of two or more. Addition of these adhesiveness-imparting agents can improve the adhesiveness to the adherend.

  A silicate can be added to the composition of the present invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability and creep resistance of the cured product obtained from the curable composition of the present invention. Further, it also has an effect of improving the adhesiveness, the water resistant adhesiveness, and the adhesive durability under high temperature and high humidity conditions. Tetraalkoxysilanes and alkylalkoxysilanes or their partially hydrolyzed condensates can be used as silicates.

  Specific examples of the silicate include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partially hydrolyzed condensates thereof.

  The partially hydrolyzed condensate of tetraalkoxysilane is more preferable because the effect of improving the restorability, durability and creep resistance of the present invention is greater than that of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to the tetraalkoxysilane by a conventional method to cause partial hydrolysis and condensation. As the partial hydrolysis-condensation product of the organosilicate compound, a commercially available product can be used. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  When a silicate is used, its amount is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B).

  Various kinds of fillers can be added to the curable composition of the present invention. As the filler, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, hydrous silicic acid, aluminum hydroxide, carbon black, hollow alumina silica fine particles (for example, trade name: PANSIL UltraSpheres ( TOLSA)) Heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolinite, silitin, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint. Resin powder such as powder, zinc oxide, activated zinc white, PVC powder, PMMA1 powder. Fibrous fillers such as asbestos, glass fibers and filaments and the like.

  As described in Japanese Patent Laid-Open No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, then enclosed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry beforehand. By using this low water content filler, it is possible to improve the storage stability, particularly in the case of a one-pack type composition.

  Further, in the case of obtaining a composition having high transparency, as described in JP-A No. 11-302527, a polymer powder made from a polymer such as methyl methacrylate or an amorphous silica is used. Etc. can be used as a filler. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using, as a filler, hydrophobic silica which is a silicon dioxide fine powder having a hydrophobic group bonded to the surface thereof. Obtainable. The surface of the silicon dioxide fine powder is generally a silanol group (-SiOH). By reacting the silanol group with an organic silicon halide or alcohol, (-SiO-hydrophobic group) is generated. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol groups present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (-SiOH) is called hydrophilic silica fine powder.

When it is desired to obtain a cured product having high adhesive strength by using these fillers, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, aluminum hydroxide. , A filler selected from, for example, colloidal calcium carbonate, ground calcium carbonate, calcined clay, clay, titanium oxide, silica-alumina ceramic filler, kaolinite, silitin and activated zinc white, and the amount thereof is the polymer (A). 1 to 200 parts by weight is preferable with respect to 100 parts by weight of the total of (B).
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. The average primary particle size of the ground calcium carbonate is preferably smaller than 3 μm, more preferably smaller than 2 μm, and most preferably smaller than 1 μm. The lower limit of the average primary particle diameter is preferably 0.05 μm. When calcium carbonate is used, the surface-treated calcium carbonate and the non-surface-treated calcium carbonate may be used alone or in combination. Surface treatment is preferable in order to increase the dispersibility of calcium carbonate, and it is preferable that the surface treatment is not performed or the surface treatment rate is low in order to obtain a cured product having high strength. As the surface treatment agent for producing the surface-treated calcium carbonate powder, palmitic acid, caprylic acid, capric acid, lauric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, etc. Examples thereof include fatty acids and unsaturated fatty acids, and carboxylic acids such as rosin acid compounds and their esters, silane compounds such as hexamethyldisilazane, chlorosilane, aminosilane, and paraffin compounds, but are not limited to these. Not necessarily. Among them, it is preferable that the surface treatment agent is a carboxylic acid, because when the curable silicone resin composition is used, the curing delay is further unlikely to occur. Further, among the carboxylic acids, saturated fatty acids or unsaturated fatty acids are particularly preferable because the curing retardation is less likely to occur. Of course, these fillers may be used alone or in combination of two or more. In order to obtain a cured product having high adhesive strength, it is preferable to use heavy calcium carbonate and colloidal calcium carbonate in combination.

  In order to improve the workability (breakage etc.) of the composition and to make the surface of the cured product matte, it is preferable to add an organic balloon or an inorganic balloon. These fillers may be surface-treated and may be used alone or in combination of two or more. The particle size of the balloon is preferably 0.1 mm or less in order to improve workability (such as sharpness). In order to make the surface of the cured product matte, the thickness is preferably 5 to 300 μm.

  The composition of the present invention is a sizing board, in particular, a ceramic-based sizing board, which is an adhesive for the joints of the outer wall of the house or the outer wall tile, or an adhesive for the outer wall tile because of the reason that the cured product has good chemical resistance. It is suitable for use in adhesives where the adhesive remains as it is, but it is desirable that the design of the outer wall and the design of the sealing material are in harmony. Particularly, as the outer wall, a high-quality outer wall has been used by spatter coating or mixing of colored aggregate or the like. When the composition of the present invention contains a scale-like or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, the cured product is in harmony with such a high-grade outer wall. However, since the chemical resistance is excellent, the appearance of this cured product is an excellent composition that lasts for a long period of time. When a granular substance is used, the surface has a sand-like or sandstone-like texture, and when a scale-like substance is used, the surface becomes uneven due to the scale-like shape.

  The preferred diameters, blending amounts, materials, etc. of the scale-like or granular substances are as described in JP-A-9-53063.

  The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and an appropriate size is used according to the material and pattern of the outer wall. It is also possible to use those having a size of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm. In the case of a scaly substance, the thickness is about 1/10 to ⅕ of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substances are premixed in the sealing main material and transported to the construction site as a sealing material, or are mixed in the sealing main material at the construction site during use.

  The scale-like or granular substance is added in an amount of about 1 to 200 parts by weight based on 100 parts by weight of the composition such as the sealing material composition and the adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As the scaly or granular substance, natural substances such as silica sand and mica, synthetic rubbers, synthetic resins, inorganic substances such as alumina are used. In order to enhance the designability when the joint portion is filled, it is colored in an appropriate color according to the material, pattern, etc. of the outer wall.

  A preferable finishing method and the like are described in JP-A-9-53063.

  Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface has a sand-like or sandstone-like texture and can be made lightweight. The preferable diameter, blending amount, material and the like of the balloon are as described in JP-A-10-251618.

  The balloon is a spherical filler having a hollow interior. The balloon can be added for the purpose of reducing the weight of the composition (reducing the specific gravity). Examples of the material for the balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. It is also possible to combine an inorganic material and an organic material, or to form a plurality of layers by stacking. Inorganic balloons, organic balloons, or composite balloons thereof can be used. Further, as the balloons to be used, the same balloon may be used, or a plurality of balloons of different materials may be mixed and used. Further, as the balloon, the one whose surface is processed or coated can be used, and the one whose surface is treated with various surface treating agents can also be used. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface-treated with a silane coupling agent.

  In order to obtain a sand-like or sandstone-like textured surface, the balloon preferably has a particle size of 0.1 mm or more. It is also possible to use those having a size of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm. If it is less than 0.1 mm, it may only increase the viscosity of the composition even if it is blended in a large amount, and the texture may not be exhibited. The blending amount of the balloon can be easily determined depending on the desired degree of sanding or sandstone-like roughness. Usually, it is desirable to mix particles having a particle size of 0.1 mm or more in a ratio of 5 to 25% by volume in the composition. If the volumetric concentration of the balloon is less than 5 vol%, there will be no roughness, and if it exceeds 25 vol%, the viscosity of the sealing material or adhesive will be high and the workability will be poor, and the modulus of the cured product will be high, and the sealing material or adhesive will be high. The basic performance of the agent tends to be impaired. The volume concentration in which the balance with the basic performance of the sealing material is particularly preferable is 8 to 22 vol%.

  When a balloon is used, an anti-slip agent as described in JP-A-2000-154368 and a surface of a cured product as described in JP-A-2001-164237 are added to an uneven state to provide a matting effect. An amidine compound for bringing into a state, in particular, a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

  Specific examples of the balloons are JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A7-111373, JP-A-9-53063, and JP-A-10. No. 251618, JP-A 2000-154368, JP-A 2001-164237, and WO 97/05201.

  Further, the heat-expandable fine particle hollow body described in JP-A-2004-51701 or JP-A-2004-66749 can be used. The heat-expandable fine particle hollow body means a low boiling point compound such as a hydrocarbon having 1 to 5 carbon atoms as a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer). It is a plastic sphere that is wrapped in a sphere with (union). By heating the adhesive part using this composition, the gas pressure inside the shell of the heat-expandable fine particle hollow body is increased, and the polymer outer shell material is softened so that the volume expands dramatically and the adhesive interface It plays the role of peeling. By adding the heat-expandable fine hollow particles, it is possible to obtain an adhesive composition which can be easily peeled without destruction of the material only by heating when unnecessary, and which can be peeled by heat without using any organic solvent.

  Even when the composition of the present invention contains particles of the cured product of the sealing material, the cured product can form irregularities on the surface and improve the design. Preferred diameters, compounding amounts, materials, etc. of the cured particles of the sealing material are as follows, as described in JP-A No. 2001-115142. The diameter is preferably 0.1 mm to 1 mm, more preferably 0.2 to 0.5 mm. The compounding amount in the curable composition is preferably 5 to 100% by weight, more preferably 20 to 50% by weight. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and the material is not limited as long as it is used as a sealing material, but a modified silicone sealing material is preferable.

  The amount of the spherical hollow body used is preferably 0.01 to 30 parts by weight, and particularly preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B). If it is less than 0.01 parts by weight, the workability is not improved, and if it exceeds 30 parts by weight, the elongation and breaking strength of the cured product tend to be low.

  If necessary, an anti-sagging agent may be added to the curable composition of the present invention in order to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when a rubber powder having a particle diameter of 10 to 500 μm as described in JP-A No. 11-349916 and an organic fiber as described in JP-A No. 2003-155389 are used, thixotropy is high. A composition having good workability can be obtained. These anti-sagging agents may be used alone or in combination of two or more kinds.

  The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of the polymers (A) and (B).

  An antioxidant (antiaging agent) can be used in the curable composition of the present invention. The use of an antioxidant can enhance the weather resistance of the cured product. Examples of antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants, with hindered phenol-based antioxidants being particularly preferred. Similarly, tinuvin 622LD, tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); All are manufactured by ADEKA Co., Ltd .; Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all above are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers described above can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B).

  A light stabilizer can be used in the curable composition of the present invention. The use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, benzoate-based compounds, and the like, and hindered amine-based compounds are particularly preferable.

  The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B).

  When a photocurable substance is added to the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use the contained hindered amine light stabilizer in order to improve the storage stability of the composition. As a tertiary amine-containing hindered amine light stabilizer, tinuvin 622LD, tinuvin 144; CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADEKA STAB LA-57, LA-62, LA-67, LA-63 (all of them above) Examples thereof include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.).

  An ultraviolet absorber can be used in the curable composition of the present invention. When an ultraviolet absorber is used, the surface weather resistance of the cured product can be increased. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, but benzotriazole-based compounds are particularly preferable, and commercial names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Examples include TINUVIN 327, TINUVIN 328, TINUVIN 329, and TINUVIN 571 (all manufactured by BASF). 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred. Further, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B).

  Various additives may be added to the curable composition of the present invention, if necessary, for the purpose of adjusting various properties of the curable composition or the cured product. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include solvents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives mentioned in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-B-64-22904. It is described in various publications such as Kai 2001-72854.

  The curable composition of the present invention can also be prepared as a one-component type in which all compounding components are previously compounded and sealed and stored, and then cured by moisture in the air after construction, and a curing catalyst and a filler are separately used as a curing agent. It is also possible to prepare a two-component type in which components such as a plasticizer and water are mixed and the compounding material and the polymer composition are mixed before use.

  When the curable composition is a one-component type, all the compounding ingredients are preliminarily compounded. Therefore, the compounding ingredients containing water should be dehydrated and dried before use, or dehydrated by reducing pressure during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to mix a curing catalyst with the main component containing a polymer having a reactive silicon group, and therefore gelation occurs even if the composition contains a small amount of water. However, dehydration drying is preferable when long-term storage stability is required. As the dehydration and drying methods, a heat drying method is suitable for solid substances such as powder, and a reduced pressure dehydration method for liquid substances or a dehydration method using synthetic zeolite, activated alumina, silica gel or the like. Alternatively, a small amount of an isocyanate compound may be blended to react the isocyanate group with water for dehydration. In addition to such dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -The storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of the dehydrating agent, in particular, the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of the polymers (A) and (B), Particularly, 0.5 to 10 parts by weight is preferable.

  The curable composition of the present invention may optionally contain a physical property adjuster for adjusting the tensile properties of the cured product produced. The physical property adjusting agent is not particularly limited, and examples thereof include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. Alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, tris (triethyl) Trialkylsilyl borates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be decreased and elongation at break can be obtained. The physical property modifiers may be used alone or in combination of two or more kinds.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has an action of lowering the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. A compound that produces trimethylsilanol is particularly preferable. Examples of the compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis include the compounds described in JP-A No. 5-117521. Further, a compound which is a derivative of an alkyl alcohol such as hexanol, octanol or decanol and which produces a silicon compound which produces R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029. A compound that is a derivative of a polyhydric alcohol having a hydroxyl group number of 3 or more, such as propane, glycerin, pentaerythritol, or sorbitol, and that produces a silicon compound that produces R ₃ SiOH such as trimethylsilanol by hydrolysis can be given.

Further, a compound which is a derivative of an oxypropylene polymer as described in JP-A-7-258534 and which produces a silicon compound which produces R ₃ SiOH such as trimethylsilanol by hydrolysis can also be mentioned. Further, a polyoxyalkylene polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group which can be converted to a monosilanol-containing compound by hydrolysis described in JP-A-6-279693 can also be used.

In the present invention, a tackifying resin can be added for the purpose of enhancing the adhesiveness or adhesion to the substrate, or as needed. The tackifying resin is not particularly limited, and a commonly used one can be used.
Specific examples include terpene-based resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenating the same, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenol. Resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

  The styrene block copolymer and its hydrogenated product are not particularly limited, and include, for example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Butylene-styrene block copolymer (SEBS), styrene-ethylene propylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), etc. are mentioned.

  Among these, the terpene-phenol resin is preferable because it has high compatibility with the polymers (A) and (B) and a high adhesion effect can be obtained. On the other hand, when color tone is important, hydrocarbon resins are preferred.

  The amount of the 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, based on 100 parts by weight of the total of the polymers (A) and (B). Is more preferable. If it is less than 2 parts by weight, it is difficult to obtain the effect of adhering or adhering to the substrate, and if it exceeds 100 parts by weight, the viscosity of the curable composition may be too high and the handling may be difficult.

  A compound containing an epoxy group can be used in the composition of the present invention. When the compound having an epoxy group is used, the restoration of the cured product can be enhanced. Examples of the compound having an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds represented by epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate. , Epoxybutyl stearate and the like. Among these, E-PS is particularly preferable. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight based on 100 parts by weight of the total of the polymers (A) and (B).

  A photocurable substance can be used in the composition of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the tackiness of the cured product and the weather resistance of the cured product can be improved. The photocurable substance is a substance that undergoes a chemical change in the molecular structure in a fairly short time by the action of light to cause a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as compounds of this type, and any commercially available compounds can be adopted. As a typical example, an unsaturated acrylic compound, polyvinyl cinnamate, or an azide resin can be used. The unsaturated acrylic compound is a monomer, an oligomer or a mixture thereof having one or several acrylic or methacrylic unsaturated groups, and is propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl. Examples include monomers such as glycol di (meth) dimethacrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (trifunctional) Aronix M305. , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (polyfunctional) Aronix M-400 can be exemplified, and particularly, compounds containing an acrylic functional group. And a compound containing an average of 3 or more functional groups in one molecule is preferable. (All of the above Aronix are products of Toagosei Chemical Industry Co., Ltd.).

  Examples of the polyvinyl cinnamate include a photosensitive resin having a cinnamoyl group as a photosensitive group, which is obtained by esterifying polyvinyl alcohol with cinnamic acid, and many polyvinyl cinnamate derivatives. Azido resin is known as a photosensitive resin having an azido group as a photosensitive group, and is usually a rubber photosensitive liquid containing a diazide compound as a photosensitizer, and also a "photosensitive resin" (March 17, 1972). Publication, published by The Printing Society of Japan, page 93-, page 106-, page 117-). These are used alone or in combination, and a sensitizer is added if necessary. You can The effect may be enhanced by adding a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine. The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B). If it is 1 part by weight or less, there is no effect of increasing the weather resistance, and if it is 20 parts by weight or more, the cured product tends to be too hard and cracking tends to occur.

  Oxygen curable materials can be used in the compositions of the present invention. An unsaturated compound that can react with oxygen in the air can be exemplified as the oxygen-curable substance, and it reacts with oxygen in the air to form a cured film near the surface of the cured product, resulting in stickiness on the surface and dust on the surface of the cured product. It acts to prevent the adhesion of dust and dirt. Specific examples of the oxygen-curing substance include a drying oil typified by tung oil and linseed oil, and various alkyd resins obtained by modifying the compound; an acrylic polymer modified with the drying oil, and an epoxy resin. Silicone resin; 1,2-polybutadiene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, 1,4-polybutadiene, and C5-C8 diene polymers. A liquid polymer or a liquid copolymer such as NBR or SBR obtained by copolymerizing a diene compound with a copolymerizable monomer such as acrylonitrile or styrene so that the diene compound is a main component, Further, various modified products thereof (maleated modified product, boil oil modified product, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, millet oil and liquid diene polymers are particularly preferable. In addition, the effect may be enhanced by using a catalyst that accelerates the oxidative curing reaction and a metal dryer together. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate and zirconium octylate, and amidine compounds. The oxygen-curable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymers (A) and (B). Parts by weight. If the amount used is less than 0.1 parts by weight, the stain resistance will not be sufficiently improved, and if it exceeds 20 parts by weight, the tensile properties of the cured product will tend to be impaired. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

  An epoxy resin can be added to the composition of the present invention. Compositions containing an epoxy resin are particularly preferred as adhesives, especially as adhesives for exterior wall tiles. As the epoxy resin, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin-type epoxy resins, epoxidized unsaturated polymers such as petroleum resins, etc., but are not limited to these, and commonly used epoxies Resins can be used. The one containing at least two epoxy groups in the molecule is preferable from the viewpoints of high reactivity during curing and easy formation of a three-dimensional network in the cured product. More preferred are bisphenol A type epoxy resins and novolac type epoxy resins. The weight ratio of these epoxy resins is polymer (A + B) / epoxy resin = 100/1 to 1/100. When the ratio of polymer (A + B) / epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin product, and the ratio of polymer (A + B) / epoxy resin is 100. When it exceeds / 1, the strength of the polymer cured product becomes insufficient. The preferred use ratio cannot be unconditionally determined because it varies depending on the application of the curable resin composition, but in the case of improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, for example. The polymer (A) and the polymer (B) are preferably used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, in the case of improving the strength of the cured product, 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of the epoxy resin is used with respect to 100 parts by weight of the total of the polymers (A) and (B). Is good.

  When an epoxy resin is added, the composition of the present invention can of course be used in combination with a curing agent that cures the epoxy resin. The epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly. Primary and secondary amines such as ethers; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic dianhydride, chlorenic anhydride, and other carboxylic anhydrides; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

  When an epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stable in the absence of water and is decomposed into primary amine and ketone by water, and the resulting primary amine serves as a room temperature curable curing agent for epoxy resin. When ketimine is used, a one-pack type composition can be obtained. Such ketimine can be obtained by a condensation reaction of an amidine compound and a carbonyl compound.

  Known amidine compounds and carbonyl compounds may be used for the synthesis of ketimine. For example, as amidine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p′-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino) Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylenepolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyl Triethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyl aminosilane such as methyldimethoxysilane; and may be used. As the carbonyl compound, aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, and other aliphatic ketones; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate and dibenzoylmethane And the like can be used.

  When an imino group is present in ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether and allyl glycidyl ether; glycidyl ester. These ketimines may be used alone or in combination of two or more kinds, and are used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin. Depends on

  To the curable composition of the present invention, a phosphorus-based plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and a flame retardant such as thermally expansive graphite can be added. The above flame retardants may be used alone or in combination of two or more.

  The flame retardant is used in the range of 5 to 200 parts by mass, preferably 10 to 100 parts by mass, based on 100 parts by mass of the polymers (A) and (B) in total.

  Various additives may be added to the curable composition of the present invention, if necessary, for the purpose of adjusting various properties of the curable composition or the cured product. Examples of such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, fungicides. And so on. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives mentioned in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-B-64-22904. It is described in various publications such as Kai 2001-72854.

  The curable composition of the present invention can also be prepared as a one-component type in which all compounding components are previously compounded and sealed and stored, and then cured by moisture in the air after construction, and a curing catalyst and a filler are separately used as a curing agent. It is also possible to prepare a two-component type in which components such as a plasticizer and water are mixed and the compounding material and the polyoxyalkylene polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferable.

  When the curable composition is a one-component type, all the compounding ingredients are pre-compounded, so the compounding ingredients containing water are dehydrated and dried before use, or dehydrated by reducing pressure during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing the polyoxyalkylene polymer having a reactive silicon group, so that the formulation contains a small amount of water. Although there is little concern about gelation, dehydration drying is preferable when long-term storage stability is required. As the dehydration / drying method, a heating / drying method is preferred for solid materials such as powder, and a vacuum dehydration method for liquid materials or a dehydration method using synthetic zeolite, activated alumina, silica gel, quick lime, magnesium oxide, etc. is there. Alternatively, a small amount of an isocyanate compound may be blended to react the isocyanate group with water for dehydration. Alternatively, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to such dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -The storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of the dehydrating agent, especially a silicon compound such as vinyltrimethoxysilane, which can react with water is 0.1 to 20 parts by weight, preferably 0 to 100 parts by weight of the total of the polymers (A) and (B). The range of 0.5 to 10 parts by weight is preferable.

  The method for preparing the curable composition of the present invention is not particularly limited, and for example, the above-mentioned components are mixed and kneaded at room temperature or under heating using a mixer, a roll, a kneader, or the like, or a suitable solvent is used in a small amount. An ordinary method such as dissolving the components by mixing and mixing the components can be adopted.

  The curable composition of the present invention is an adhesive, a sealing material for structures, ships, automobiles, roads, etc., an adhesive, a molding agent, a vibration damping material, a vibration damping material, a soundproofing material, a foam material, a paint, a spraying material. It can be used as a film waterproofing agent. The cured product obtained by curing the curable composition of the present invention can obtain good adhesiveness to various adherends, and thus is more preferably used as a sealing material or an adhesive.

  Also, electrical / electronic component materials such as solar cell backside encapsulation materials, electrical insulation materials such as electric wire / cable insulation coating materials, elastic adhesives, contact adhesives, spray-type sealing materials, crack repair materials, and tiling. Adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electric and electronic use, films, gaskets, various molding materials, and rustproof / waterproof encapsulants for meshed glass and laminated glass end faces (cut parts), It can be used for various purposes such as a liquid sealant used in automobile parts, electric parts, various machine parts and the like. Further, it can be adhered to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc. alone or with the aid of a primer, and thus can be used as various types of sealing composition and adhesive composition. . Further, the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tile installation, an adhesive for stone installation, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for floor finishing. Adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, direct glazing sealing materials, double glazing sealing materials, SSG method sealing materials, or building working joint sealing materials, It can also be used as

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.
(Synthesis example 1)
Using ethylene glycol monoallyl ether as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight was about 7,000 (Tosoh HLC-8120GPC was used as the liquid delivery system, and the column was manufactured by Tosoh. Polyoxypropylene having a polystyrene-reduced molecular weight measured using TSK-GEL H type and THF as a solvent was obtained. Subsequently, 1.0 molar equivalent of a solution of NaOMe in methanol was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene to distill off methanol, and then 1.0 molar equivalent of methacrylic acid chloride was added to the hydroxyl group. The resulting mixture was added and reacted at 23 ° C. for 2 hours to obtain a crude product.
The crude product was diluted with hexane, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Chemical Co., Ltd.) and magnesium oxide were added, and the mixture was stirred for 1 hour. The filtrate was concentrated under reduced pressure to obtain an oxypropylene polymer having an allyl group at one end and a methacryloyl group at one end. 72 ppm of platinum divinyldisiloxane complex (3% by weight of isopropanol solution in terms of platinum) and 200 ppm of p-methoxyphenol as a polymerization inhibitor were added to 100 parts by weight of the obtained polymer, and dimethoxymethylsilane 2.3 was added while stirring. Parts by weight are slowly added dropwise and reacted at 90 ° C. for 2 hours to give a dimethoxymethylsilyl group at one end (0.86 silicon groups on average per molecule) and a methacryloyl group at the other end ( A linear macromonomer (a-1) having an average of 0.8 methacryloyl groups per molecule) and a number average molecular weight of 7,000 was obtained.

(Synthesis example 2)
45.9 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer and heated to 105 ° C. under a nitrogen atmosphere. There, 35.0 parts by weight of methyl methacrylate, 25.0 parts by weight of stearyl methacrylate, 30 parts by weight of the macromonomer (a-1) synthesized in Synthesis Example 1, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, A mixed solution of 4.0 parts by weight of 3-mercaptopropyltrimethoxysilane and 2.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) in 25.2 parts by weight of isobutanol was taken for 5 hours. Was dropped. Polymerization is further performed at 105 ° C. for 2 hours, the average number of silicon groups per molecule is 2.3, the number of macromonomers introduced per molecule is 0.2, and the number average molecular weight is 3,600. Isobutanol solution (solid content 60%) of reactive silicon group-containing (meth) acrylic acid ester polymer (A-1) having a weight average molecular weight of 12,800 (measured by the same method as in Synthesis Example 1). Got

(Synthesis example 3)
59.5 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer and heated to 90 ° C. under a nitrogen atmosphere. 14.5 parts by weight of methyl methacrylate, 45.0 parts by weight of butyl acrylate, 14.3 parts by weight of stearyl methacrylate, 25 parts by weight of the macromonomer (a-1) synthesized in Synthesis Example 1, and 3-methacryloxypropyldimethoxy. A mixed solution of 1.2 parts by weight of methylsilane and 0.56 parts by weight of 2,2′-azobis (2-methylbutyronitrile) in 7.5 parts by weight of isobutanol was added dropwise over 5 hours. Polymerization is further carried out at 90 ° C. for 2 hours, the average number of silicon groups per molecule is 1.7, the number of macromonomers introduced per molecule is 0.9, and the number average molecular weight is 18,400. Isobutanol solution (solid content 60%) of reactive silicon group-containing (meth) acrylate polymer (A-2) having a weight average molecular weight of 51,300 (measured by the same method as in Synthesis Example 1). Got

(Synthesis example 4)
45.9 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer and heated to 105 ° C. under a nitrogen atmosphere. There, 35.0 parts by weight of methyl methacrylate, 30 parts by weight of butyl acrylate, 25.0 parts by weight of stearyl methacrylate, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 4.0 parts by weight of 3-mercaptopropyltrimethoxysilane. Part and 2.52 parts by weight of 2,2′-azobis (2-methylbutyronitrile) dissolved in 25.2 parts by weight of isobutanol were added dropwise over 5 hours. Polymerization was further carried out at 105 ° C. for 2 hours, and the average number of silicon groups per molecule was 2.1, the number average molecular weight was 3,600, and the weight average molecular weight was 7,400 (measured in the same manner as in Synthesis Example 1). A solution of the reactive silicon group-containing (meth) acrylic acid ester polymer (P-1) in isobutanol (solid content 60%) was obtained.

(Synthesis example 5)
59.5 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer and heated to 90 ° C. under a nitrogen atmosphere. There, 14.5 parts by weight of methyl methacrylate, 68.2 parts by weight of butyl acrylate, 14.9 parts by weight of stearyl methacrylate, 2.4 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, and 2,2'-azobis (2 -Methyl butyronitrile) (0.56 parts by weight) dissolved in 7.5 parts by weight of isobutanol was added dropwise over 5 hours. Polymerization was further carried out at 90 ° C. for 2 hours, and the number of silicon groups per molecule was 1.7 on average, the number average molecular weight was 16,900, and the weight average molecular weight was 44,100 (measured in the same manner as in Synthesis Example 1). To obtain a solution of the reactive silicon group-containing (meth) acrylic acid ester polymer (P-2) in isobutanol (solid content 60%).

(Synthesis example 6)
Using polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of about 28,500 (in the same manner as in Synthesis Example 1). (Measured) was obtained. Subsequently, 1.0 molar equivalent of NaOMe in methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene to distill off methanol, and then 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group. The mixture was added and reacted at 130 ° C. for 2 hours. Then, 0.28 equivalent of a sodium methoxide solution in methanol was added to remove methanol, and 1.79 molar equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, the water was removed again by centrifugation, and then hexane was removed by devolatization under reduced pressure. As described above, a polyoxypropylene polymer having an average of 2.1 carbon-carbon unsaturated bonds at one terminal site was obtained. Next, 72 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained polymer, and 2.9 parts by weight of triethoxysilane was slowly added dropwise with stirring. The reaction was carried out at 90 ° C for 2 hours. Furthermore, by adding 20 parts by weight of methanol and 12 ppm of HCl to convert the ethoxy group at the terminal into a methoxy group, the terminal is a trimethoxysilyl group, the average number of silicon groups per molecule is 3.2, and the number average molecular weight is A linear reactive silicon group-containing polyoxypropylene polymer (B-1) having a molecular weight of 28,500 was obtained.

(Synthesis example 7)
Using polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 28,500 (calculated by the same method as in Synthesis Example 1). Was obtained). Subsequently, 1.2 times equivalent of a methanol solution of NaOMe was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene diol to distill off methanol, and 1.5 times equivalent of 3-chloro-1-propene was added. Then, the terminal hydroxyl group was converted to an allyl group. Next, 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropyl alcohol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer, and 0.96 parts by weight of dimethoxymethylsilane was added while stirring. Part was slowly added dropwise, and after reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a terminal of dimethoxymethylsilyl group and an average of 1 silicon group per molecule. A linear reactive silicon group-containing polyoxypropylene polymer (B-2) having a number of 6 and a number average molecular weight of 28,500 was obtained.

(Example 1)
50.0 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (B-1) obtained in Synthesis Example 6 and the reactive silicon group-containing (meth) acrylic polymer (A- obtained in Synthesis Example 2) 83.3 parts by weight of the isobutanol solution of 1) was mixed and the isobutanol was distilled off under reduced pressure to obtain a polymer mixture having a polymer weight ratio (A-1) / (B-1) = 50/50. Obtained.

(Evaluation)
The viscosity of the prepared polymer mixture and the tensile properties of the cured product were measured by the methods described below.

(viscosity)
The viscosity of the blend was measured with an E-type viscometer (manufactured by Tokyo Keiki, measuring cone: 3 ° C x R14) at 23 ° C and 50% relative humidity. The results are shown in Table 2.

(Tensile properties)
To 100 parts by weight of the total of the polymers (A-1) and (B-1), 1 part by weight of vinyltrimethoxysilane (manufactured by Momentive Co., trade name: A-171), N- (2-amino) Ethyl) -3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603) 2 parts by weight, dioctyl tin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-810) 0 After adding 2 parts by weight, they were mixed well. The obtained compound was filled in a polyethylene frame having a thickness of 3 mm so as not to contain bubbles, and cured at 23 ° C. and 50% relative humidity for 3 days, and further at 50 ° C. for 4 days to obtain a cured product. From the obtained cured product, No. 7 dumbbell was punched out in accordance with JIS K 6251, and a tensile test (pulling speed 200 mm / min, 23 ° C., relative humidity 50%) was performed, and a modulus at 100% elongation (M100), The strength at break (TB) and the elongation at break (EB) were measured. The results are shown in Table 2.

In Table 2, it can be seen from the comparison between Example 1 and Comparative Example 1 and between Example 2 and Comparative Example 2 that the curable composition containing the polymer (A) has excellent tensile physical properties.

Claims (7)

Formula ^{_{(1): - SiR 1 a}} X 3-a (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X's each independently represent a hydroxyl group or a hydrolyzable group. A represents 0 or 1.)
A monomer having a reactive silicon group and having a polymerizable unsaturated group, and a number average molecular weight of 1,000 having a reactive silicon group and an acryloyl group or a methacryloyl group represented by the general formula (1). To 30,000 oxyalkylene macromonomer (a) as a constituent monomer, (meth) acrylic acid ester polymer (A) , and polyoxyalkylene polymer (B) having a reactive silicon group Curable composition containing. The curable composition according to claim 1, wherein the content of the oxyalkylene macromonomer (a) in all monomers constituting the (meth) acrylic acid ester polymer (A) is 1 to 50% by weight. Stuff. Curing according to claim 1 or 2, wherein the content of the (meth) acrylic acid ester-based monomer in all the monomers constituting the (meth) acrylic acid ester-based polymer (A) is 50 to 90% by weight. Sex composition. 4. The average number of oxyalkylene macromonomers (a) in one molecule of (meth) acrylic acid ester-based polymer (A) is 0.01 or more and 2.0 or less. A curable composition according to item. A sealing material composition containing the curable composition according to claim 1. An adhesive composition containing the curable composition according to any one of claims 1 to 4 . A cured product of the curable composition according to any one of claims 1 to 4 .