JP2020158733A - Curable composition and cured product - Google Patents

Abstract

To provide a curable composition comprising a polyoxyalkylene-based polymer having a reactive silyl group and a (meth)acrylic ester-based polymer having a reactive silyl group, which can form a cured product exhibiting high elongation while having high strength.SOLUTION: There is provided a curable composition comprising a polyoxyalkylene-based polymer (A) having a reactive silyl group and a (meth)acrylic ester-based polymer (B) having a reactive silyl group. The average number of reactive silyl groups bonded to a terminal of the polymer skeleton in one molecule of the polymer (B) is 0.30 or more and 1.00 or less and the average number of reactive silyl groups bonded to the inside of the polymer skeleton in one molecule of the polymer (B) is 0.01 or more and 0.20 or less.SELECTED DRAWING: None

Description

The present invention relates to a curable composition and a cured product.

An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and a silicon-containing group capable of forming a siloxane bond (hereinafter referred to as "reactive silyl group") is known as a moisture-reactive polymer. It is contained in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and is used in a wide range of fields.

In particular, a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid ester polymer having a reactive silyl group are blended for use in applications such as a highly weather resistant sealing material and an elastic adhesive. Curable compositions are known (see, for example, Patent Documents 1 to 4).

International Publication No. 2011/152002 International Publication No. 2017/05/7719 Japanese Unexamined Patent Publication No. 2017-066349 Japanese Unexamined Patent Publication No. 2003-313418

The cured product obtained from a curable composition obtained by blending a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid ester polymer having a reactive silyl group exhibits high strength, while exhibiting high strength. In some cases, the elongation was not sufficient.

In view of the above situation, the present invention has a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid having a reactive silyl group, which can form a cured product showing high elongation while having high strength. An object of the present invention is to provide a curable composition containing an ester-based polymer.

As a result of diligent research to solve the above problems, the present inventors have found that the average number and weight of reactive silyl groups at the ends of the polymer skeleton per molecule of the (meth) acrylic acid ester-based polymer (B). We have found that the above problems can be solved by setting the average number of reactive silyl groups inside the coalesced skeleton within a specific range, and have arrived at the present invention.

That is, the present invention has the following general 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 represents a hydroxyl group or a hydrolyzable group. A is 0, 1 or 2. R ¹ or X. When there are a plurality of polyoxyalkylene-based polymers (A) having a reactive silyl group represented by (they may be the same or different), and the following general formula (2):
−SiR ² _b Y _3-b (2)
(In the formula, R ² represents an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. B is 0, 1 or 2. Multiple R ² or Y. When present, they may be the same or different), comprising a (meth) acrylic acid ester-based polymer (B), having a reactive silyl group represented by (), and a (meth) acrylic acid ester-based polymer. The average number of reactive silyl groups bonded to the ends of the polymer skeleton in one molecule of the polymer (B) is 0.30 or more and 1.00 or less, and the (meth) acrylic acid ester-based polymer (B) 1 The present invention relates to a curable composition in which the average number of reactive silyl groups bonded to the inside of the polymer skeleton in the molecule is 0.01 or more and 0.20 or less. Preferably, the average number of reactive silyl groups bonded to the inside of the polymer skeleton in one molecule of the (meth) acrylic acid ester-based polymer (B) is 0.03 or more and 0.15 or less. Preferably, the average number of reactive silyl groups bonded to the ends of the polymer skeleton in one molecule of the (meth) acrylic acid ester-based polymer (B) is 0.90 or more and 1.00 or less. Preferably, the total proportion of alkyl methacrylate in the constituent monomer units of the (meth) acrylic acid ester-based polymer (B) is 70% by weight or more and 85% by weight or less, and the alkyl has 1 carbon atom. It is an unsubstituted alkyl group of ~ 4. Preferably, the proportion of methyl methacrylate in the constituent monomer units of the (meth) acrylic acid ester-based polymer (B) is 70% by weight or more and 85% by weight or less. Preferably, the weight ratio of the polyoxyalkylene polymer (A): (meth) acrylic acid ester polymer (B) is 75:25 to 50:50. Preferably, the polyoxyalkylene polymer (A) has a branched-chain polymer skeleton.
The present invention also relates to a cured product obtained by curing the curable composition.

According to the present invention, a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid ester-based polymer having a reactive silyl group capable of forming a cured product showing high elongation while having high strength. A curable composition containing coalescence can be provided.

Embodiments of the present invention will be described in detail below.
(Polyoxyalkylene polymer (A))
The curable composition of the present invention contains a polyoxyalkylene polymer (A) having a reactive silyl group. Since the polyoxyalkylene polymer (A) has the reactive silyl group, it exhibits curability based on the hydrolysis and dehydration condensation reaction of the reactive silyl group.

The polyoxyalkylene polymer (A) has a polymer skeleton of polyoxyalkylene and a terminal structure bonded to the end of the polymer skeleton. The polymer skeleton refers to a polymer main chain composed of oxyalkylene repeating units. The polymer skeleton of the polyoxyalkylene polymer (A) may be a linear one or a branched chain one. The branched-chain polymer skeleton is preferable because the cured product of the curable composition has high strength. The linear polymer skeleton can be formed by using an initiator having two hydroxyl groups in one molecule in the polymerization method for forming the polymer skeleton, and the branched polymer skeleton can be formed. It can be formed by using an initiator having three or more hydroxyl groups in one molecule.

The polymer skeleton is a polymer skeleton composed of only a plurality of oxyalkylene repeating units linked to each other, or is derived from an initiator used during polymerization in addition to the plurality of oxyalkylene repeating units. It is preferable that the polymer skeleton contains a structure and is composed only of these. Here, the oxyalkylene repeating unit refers to a repeating unit constituting a polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

The polymer skeleton of the polyoxyalkylene is not particularly limited, and for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxy. Butylene copolymer and the like can be mentioned. Polyoxypropylene is preferred. As the polymer skeleton, only one type may be used, or two or more types may be used in combination.

The terminal structure refers to a site that does not contain an oxyalkylene repeating unit constituting the polymer skeleton of polyoxyalkylene and is bonded to the end of the polymer skeleton. The terminal structure is preferably bonded to an oxyalkylene unit located at the end of the polymer skeleton via an oxygen atom. Further, it is preferable that the reactive silyl group contained in the polyoxyalkylene polymer (A) is contained in the terminal structure.

The reactive silyl group contained in the polyoxyalkylene polymer (A) has the following general formula (1):
−SiR ¹ _a X _3-a (1)
It is represented by.

R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Here, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N, N-diethylamino group. ..

The R ^1, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, tert- butyl group, n- hexyl group ,, a 2-ethylhexyl group, an unsubstituted such n- dodecyl group Alkyl group of: Substituent alkyl group such as chloromethyl group, methoxymethyl group, N, N-diethylaminomethyl group; unsaturated hydrocarbon group such as vinyl group, isopropenyl group, allyl group; cycloalkyl group such as cyclohexyl group; Aryl groups such as phenyl group, toluyl group and 1-naphthyl group; aralkyl groups such as benzyl group and the like can be mentioned. It is preferably a substituted or unsubstituted alkyl group, more preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, still more preferably a methyl group or a methoxymethyl group, and particularly preferably a methyl group. Is the basis. As R ¹ , only one type of group may be used, or two or more types of groups may be used in combination.

X represents a hydroxyl group or a hydrolyzable group. Examples of X include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like. The above-mentioned alkoxy group and the like may have a substituent. An alkoxy group is preferable, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, a methoxy group and an ethoxy group are further preferable, and a methoxy group is particularly preferable, because the hydrolyzability is mild and easy to handle. As X, only one type of group may be used, or two or more types of groups may be used in combination.

A in the formula (1) is 0, 1 or 2. It is preferably 0 or 1. It is more preferably 1 in terms of the balance between the curability of the curable composition and the physical properties of the cured product.

Examples of the reactive silyl group represented by the general formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, and a methyldi. Ethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) ) Dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group and the like. Among them, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) ) Dimethoxysilyl group and the like. From the viewpoint of reactivity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are more preferable. From the viewpoint of stability, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are more preferable. Further, a trimethoxysilyl group, a triethoxysilyl group and a methyldimethoxysilyl group are more preferable because they are easy to produce. Of these, the methyldimethoxysilyl group is most preferable.

In the polyoxyalkylene polymer (A), the terminal structure having a reactive silyl group is not particularly limited, but as a typical one, the terminal represented by the following general formula (3) or (4) is represented. The structure can be mentioned.

-O-R ^3- CH (R ⁴ ) -CH _2- SiR ¹ _a X _3-a (3)
In the formula, R ³ represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁴ represents hydrogen or an alkyl group having 1 to 6 carbon atoms. The oxygen at the left end indicates oxygen in the oxyalkylene unit located at the end of the polymer skeleton. R ¹ , R ² , X, and a are the same as those described above for equation (1).

The R ^3, preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms. As the hydrocarbon group, an alkylene group is preferable, and a methylene group, an ethylene group, a propylene group, and a butylene group can be used. Methylene groups are particularly preferred.

The R ^4, preferably is hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include hydrogen, methyl group, ethyl group, propyl group, butyl group and the like. As R ⁴ , hydrogen, a methyl group and an ethyl group are preferable, and hydrogen and a methyl group are more preferable. In particular, since the improved average ratio of the number of reactive silyl groups to the number of ends of the polymer backbone as described above, a methyl group is preferable as R ^4.

Wherein, ^{R 5} is a direct bond or a divalent linking group having 1 to 6 carbon atoms. R ⁶ is hydrogen, or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. The oxygen at the left end indicates oxygen in the oxyalkylene unit located at the end of the polymer skeleton formed by connecting a plurality of oxyalkylene units. R ¹ , R ² , R ³ , R ⁴ , X, and a are the same as those described above for equations (1) and (3).

R ⁵ may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. It is preferably CH ₂ OCH ₂ , CH ₂ O, and CH ₂ , and more preferably CH ₂ OCH ₂ .

As R ⁶ , hydrogen or a hydrocarbon group having 1 to 5 carbon atoms is preferable, hydrogen or a hydrocarbon group having 1 to 3 carbon atoms is more preferable, and hydrogen or a hydrocarbon group having 1 to 2 carbon atoms is further preferable. preferable. A hydrogen atom and a methyl group are particularly preferable, and a hydrogen atom is most preferable.

The terminal structure represented by the general formula (4) represents one terminal structure bonded to one terminal of the polymer skeleton. Although two or more reactive silyl groups are shown in formula (4), formula (4) does not show two or more ends, but two or more reactive in one terminal structure. It indicates that a silyl group is present. Further, the formula (4) does not include a polymer skeleton composed of an oxyalkylene repeating unit. That is, the n structures in parentheses in the formula (4) do not correspond to the oxyalkylene repeating unit in the polymer skeleton.

The number average molecular weight of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000 in terms of polystyrene-equivalent molecular weight in GPC. It is preferably 3,000 to 30,000. When the number average molecular weight is 3,000 or more, the relative amount of the reactive silyl group with respect to the entire polymer is in an appropriate range, which is desirable from the viewpoint of production cost. Further, when the number average molecular weight is 100,000 or less, it is easy to achieve a desired viscosity from the viewpoint of workability. The number average molecular weight can be determined by GPC measurement in terms of polystyrene.

The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and the weight average molecular weight obtained in terms of polystyrene by GPC measurement.

<Method for producing polyoxyalkylene polymer (A)>
Next, a method for producing the polyoxyalkylene polymer (A) will be described. The polyoxyalkylene-based polymer (A) is a reaction having reactivity with the olefin group after introducing an olefin group into the hydroxyl group-terminated polyoxyalkylene-based polymer (C) by utilizing the reactivity of the hydroxyl group. It can be produced by reacting a compound containing a reactive silyl group to introduce a reactive silyl group.

Hereinafter, embodiments of the method for producing the polyoxyalkylene polymer (A) will be described in detail, but the method for producing the polyoxyalkylene polymer (A) is not limited to the following description.

(polymerization)
The polymer skeleton of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, whereby the hydroxyl-terminated polyoxyalkylene polymer (C) can be formed. Is obtained. The specific polymerization method is not particularly limited, but since a hydroxyl group-terminated polymer having a small molecular weight distribution (Mw / Mn) can be obtained, a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex. Is preferable.

The initiator having a hydroxyl group is not particularly limited, and for example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, and low molecular weight polyoxypropylene. Examples thereof include organic compounds having one or more hydroxyl groups, such as monoallyl ether and low molecular weight polyoxypropylene monoalkyl ether.

The epoxy compound is not particularly limited, and examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferable.

(Reaction with alkali metal salts)
In introducing an olefin group into the hydroxyl group-terminated polyoxyalkylene polymer (C), first, an alkali metal salt is allowed to act on the hydroxyl group-terminated polyoxyalkylene polymer (C) to make the terminal hydroxyl group a metaloxy group. It is preferable to convert to. Further, a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. As a result, the metaloxy group-terminated polyoxyalkylene polymer (D) is formed.

The alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium methoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide are preferable, and sodium methoxide and sodium tert are preferable. -Butoxide is more preferred. Sodium methoxide is particularly preferred in terms of availability, and sodium tert-butoxide is particularly preferred in terms of reactivity. The alkali metal salt may be subjected to the reaction in a state of being dissolved in a solvent.

The amount of the alkali metal salt used is not particularly limited, but the molar ratio of the hydroxyl-terminated polyoxyalkylene polymer (C) to the hydroxyl group is preferably 0.5 or more, more preferably 0.6 or more, and 0. 7 or more is more preferable, and 0.8 or more is even more preferable. The molar ratio is preferably 1.2 or less, more preferably 1.1 or less. When the alkali metal salt is used within the above range, the conversion reaction of the hydroxyl group to the metal oxy group easily proceeds sufficiently, and it is possible to prevent the alkali metal salt from remaining as an impurity and the side reaction from proceeding.

The alkali metal salt is used to convert the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer (C) into a metaloxy group, but in order to efficiently proceed with this conversion reaction, water or polyoxy is used. It is preferable to remove a substance having a hydroxyl group other than the alkylene polymer from the reaction system in advance. For removal, a known method may be used, and for example, heat evaporation, vacuum evaporation, spray vaporization, thin film evaporation, azeotropic evaporation and the like can be used.

The temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 145 ° C. or lower. The time for the alkali metal salt to act is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.

(Reaction with electrophile (E))
By allowing the electrophile (E) having an olefin group to act on the metaloxy group-terminated polyoxyalkylene polymer (D) obtained as described above, the metaloxy group has a structure containing an olefin group. Can be converted to. As a result, a polyoxyalkylene polymer (F) having an olefin group in the terminal structure is formed.

The electrophilic agent (E) having an olefin group is particularly limited as long as it is a compound capable of reacting with the metaloxy group of the polyoxyalkylene polymer (D) and introducing an olefin group into the polyoxyalkylene polymer. However, examples thereof include organic halides having an olefin group and epoxy compounds having an olefin group.

The organic halide (E1) having an olefin group, which is one aspect of the electrophile (E), reacts with the metaloxy group by a halogen substitution reaction to form an ether bond, thereby forming a polyoxyalkylene-based weight. A structure containing an olefin group can be introduced as the terminal structure of the coalescence. The organic halide (E1) having an olefin group is not limited, but the following general formula (5):
Z-R ^3- C (R ⁴ ) = CH ₂ (5)
Can be represented by. In the formula, R ³ and R ⁴ are the same groups as R ³ and R ⁴ described above for the general formula (3), respectively. Z represents a halogen atom. When the reactive silyl group described later is introduced into the polyoxyalkylene polymer (F) having an olefin group in the terminal structure obtained by reacting the organic halide (E1), the above-mentioned general The terminal structure represented by the formula (3) can be formed.

Specific examples of the organic halide (E1) having an olefin group are not particularly limited, but vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, Examples include metallyl iodide. Allyl chloride and methallyl chloride are preferable because of ease of handling. Further, since the average ratio of the number of reactive silyl groups to the number of terminals of the polymer skeleton described above is improved, metallyl chloride, metallic bromide, and metallic iodide are preferable.

The amount of the organic halide (E1) having an olefin group added is not particularly limited, but the molar ratio of the organic halide (E1) to the hydroxyl group of the polyoxyalkylene polymer (C) is 0.7 or more. Preferably, 1.0 or more is more preferable. The molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The temperature at which the organic halide having an olefin group (E1) is reacted with the metaloxy group-terminated polyoxyalkylene polymer (D) is preferably 50 ° C. or higher and 150 ° C. or lower, and 110 ° C. or higher and 140 ° C. or lower. Is more preferable. The reaction time is preferably 10 minutes or more and 5 hours or more, and more preferably 30 minutes or more and 3 hours or less.

Another embodiment of the electrophile (E), the epoxy compound (E2) having an olefin group, reacts with the metaloxy group by a ring-opening addition reaction of the epoxy group to form an ether bond to form a polyoxy. A structure containing an olefin group and a hydroxyl group can be introduced as the terminal structure of the alkylene polymer. In the ring-opening addition reaction, one or more epoxy compounds (E2) are added to one metaloxy group by adjusting the amount of the epoxy compound (E2) used for the metaloxy group and the reaction conditions. Can be made to.

The epoxy compound (E2) having an olefin group is not limited, but the following general formula (6):

Can be represented by. In the formula, R ⁵ and R ⁶ are the same groups as R ⁵ and R ⁶ described above for the general formula (4), respectively.

Specific examples of the epoxy compound (E2) having an olefin group are not particularly limited, but allyl glycidyl ether, metallicyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monooxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is preferable. Especially preferable.

The amount of the epoxy compound (E2) having an olefin group added can be any amount in consideration of the amount of the olefin group introduced into the polymer and the reactivity. In particular, the molar ratio of the epoxy compound (E2) to the hydroxyl group of the polyoxyalkylene polymer (C) is preferably 0.2 or more, more preferably 0.5 or more. The molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The reaction temperature at the time of cycloaddition reaction of the epoxy compound (E2) having an olefin group with the metaloxy group-terminated polyoxyalkylene polymer (D) is 60 ° C. or higher and 150 ° C. or lower. It is preferably 110 ° C. or higher and 140 ° C. or lower, more preferably.

When the epoxy compound (E2) having an olefin group is allowed to act on the metaloxy group-terminated polyoxyalkylene polymer (D) as described above, a new metaloxy group is generated by ring opening of the epoxy group. Therefore, after the epoxy compound (E2) is allowed to act, the above-mentioned organic halide having an olefin group (E1) can be continuously acted on. As the organic halide (E1) having an olefin group used in this embodiment, the same compound as described above can be used, and the amount and reaction temperature thereof are the same as described above. This method is preferable because the amount of the olefin group introduced into the polymer and the amount of the reactive silyl group introduced can be further increased. The reactive silyl group described below with respect to the polyoxyalkylene polymer (F) having an olefin group in the terminal structure obtained by the method of using the epoxy compound (E2) and the organic halide (E1) in combination. When the above is carried out, the terminal structure represented by the general formula (4) can be formed.

(Introduction of reactive silyl group)
The polyoxyalkylene polymer (F) having an olefin group in the terminal structure obtained as described above is subjected to a hydrosilylation reaction with a hydrosilane compound (G) having a reactive silyl group, whereby the polymer is reactive silyl. The group can be introduced. As a result, the polyoxyalkylene polymer (A) having a reactive silyl group is produced. The hydrosilylation reaction has the advantages that it can be easily carried out, the amount of the reactive silyl group introduced can be easily adjusted, and the physical properties of the obtained polymer are stable.

Specific examples of the hydrosilane compound (G) having a reactive silyl group include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, and bis (chloromethyl). ) Halosilanes such as chlorosilane, (methoxymethyl) dichlorosilane, (dimethoxymethyl) dichlorosilane, bis (methoxymethyl) chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyl Dimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (Methoxymethyl) dimethoxysilane, bis (methoxymethyl) methoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane, (N, N- Diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [(chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyl Oxy] dimethylsilane, [(methoxymethyl) diemethoxysilyloxy] dimethylsilane, [(diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, [(3,3,3-trifluoropropyl) dimethoxysilyloxy] dimethylsilane, etc. Alkoxysilanes; Asyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; Ketoximatesilanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane, triisopropeniloxisilane , (Chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane and other isopropenyloxysilanes (deacetone type) and the like.

The amount of the hydrosilane compound (G) having a reactive silyl group may be appropriately set in consideration of the amount of the olefin group contained in the polyoxyalkylene polymer (F). Specifically, the molar ratio of the hydrosilane compound (G) to the olefin group of the polyoxyalkylene polymer (F) is preferably 0.05 or more and 10 or less, and 0.3 or more and 3 or less from the viewpoint of reactivity. More preferred. The molar ratio is more preferably 0.5 or more, and particularly preferably 0.7 or more, in that the modulus value of the cured product of the obtained polyoxyalkylene polymer (A) can be increased. On the other hand, from the viewpoint of economy, the molar ratio is more preferably 2.5 or less, and particularly preferably 2 or less.

The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof and the like are known, and these can be used. Specifically, a carrier such as alumina, silica, or carbon black on which platinum is supported; platinum chloride acid; a platinum chloride acid complex composed of platinum chloride acid and alcohol, aldehyde, ketone, or the like; a platinum-olefin complex [for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ), Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ]; Platinum-vinylsiloxane complex [eg Pt {(vinyl) Me ₂ SiOSiMe ₂ (vinyl)}, Pt { Me (vinyl) SiO} ₄ ]; Platinum-phosphine complex [eg Ph (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ]; Platinum-phosphite complex [eg Pt {P (OPh) ₃ } ₄ ] and the like. Be done. From the viewpoint of reaction efficiency, platinum catalysts such as platinum chloride acid and platinum vinyl siloxane complex are preferable.

The hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the polyoxyalkylene polymer (F), the hydrosilane compound (G), and the hydrosilylation catalyst, and the reaction. In order to easily control the temperature of the system and add a hydrosilylation catalyst, an organic solvent may be added.

The temperature conditions for the hydrosilylation reaction are not particularly limited and can be appropriately set by those skilled in the art, but the reaction under heating conditions is preferable for the purpose of lowering the viscosity of the reaction system and improving the reactivity, specifically. , The reaction at 50 ° C. to 150 ° C. is more preferable, and the reaction at 70 ° C. to 120 ° C. is further preferable. The reaction time may be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction between the polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, and more preferably 3 hours or less.

The hydrosilylation reaction may also be carried out in the presence of an orthocarboxylic acid trialkyl ester. This makes it possible to suppress thickening during the hydrosilylation reaction and improve the storage stability of the obtained polymer.

Examples of the orthocarboxylic acid trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Preferred are trimethyl orthoformate and trimethyl orthoacetate.

When the orthocarboxylic acid trialkyl ester is used, the amount used is not particularly limited, but is preferably about 0.1 to 10 parts by weight, preferably about 0.1 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A). About 3 parts by weight is more preferable.

As another method for producing the polyoxyalkylene polymer (A), the compound (H) having a reactive silyl group and an isocyanate group in one molecule with respect to the hydroxyl group-terminated polyoxyalkylene polymer (C). A method of introducing a reactive silyl group by forming a urethane bond can also be applied. Also by this method, the polyoxyalkylene polymer (A) having a reactive silyl group can be produced.

The compound (H) having a reactive silyl group and an isocyanate group in one molecule includes an isocyanate group capable of a urethanization reaction with a hydroxyl group of the polyoxyalkylene polymer (C) and a reactive silyl group. The compound is not particularly limited as long as it is contained in the molecule, but specific examples thereof include (3-isocyanatepropyl) trimethoxysilane, (3-isocyanatepropyl) dimethoxymethylsilane, (3-isocyanatepropyl) triethoxysilane, and (3-isocyanatepropyl) triethoxysilane. Examples thereof include 3-isocyanatepropyl) diethoxymethylsilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) dimethoxymethylsilane, and (isocyanatemethyl) diethoxymethylsilane.

The amount of the compound (H) having a reactive silyl group and an isocyanate group in one molecule may be appropriately determined in consideration of the amount of the hydroxyl group of the polyoxyalkylene polymer (C). Specifically, the molar ratio of the isocyanate group of the compound (H) to the hydroxyl group of the polyoxyalkylene polymer (C) is preferably 0.5 or more, more preferably 0.8 or more, and 0.9. The above is more preferable. The upper limit of the amount of compound (H) used is not particularly limited, and the molar ratio is preferably 1 or less, but may exceed 1. When the molar ratio exceeds 1, the excess compound (H) may be removed by a treatment such as devolatile under reduced pressure after the urethanization reaction, or may be reacted with an active hydrogen group-containing compound or the like to form another compound. It may be converted or may remain in the polyoxyalkylene polymer (A). The compound (H) remaining in the polyoxyalkylene polymer (A), or a derivative thereof, can act as a silane coupling agent.

The urethanization reaction may be carried out without using the urethanization catalyst, but may be carried out in the presence of the urethanization catalyst for the purpose of improving the reaction rate or the reaction rate. Examples of such urethanization catalysts include Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Sanders and Frisch, Interscience Publicly known, and known catalysts such as Polyurethane, New York 19 A catalyst can be used. Specific examples thereof include, but are not limited to, organic tin compounds, bismuth compounds, base catalysts such as organic amines, and the like.

Among the known urethanization catalysts, as highly active catalysts, tin octylate, tin stearate, dibutyltin dioctate, dibutyltin dioleyl malate, dibutyltin dibutylmalate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl -1,3-dilauryloxycarbonyl distanoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltinbis (o-phenylphenoxide), dibutyltin oxide, dibutyltinbis (triethoxysilicate), dibutyltin distearate, dibutyltinbis (Isononyl-3-mercaptopropionate), dibutyltinbis (isooctylmercaptopropionate), dibutyltinbis (isooctylthioglycolate), dioctyltinoxide, dioctyltindilaurate, dioctyltindiacetate, dioctyltindiversate Organic tin compounds such as are preferred. Further, a catalyst having low activity with respect to the reactive silyl group is preferable, and from this viewpoint, dibutyltinbis (isononyl-3-mercaptopropionate), dibutyltinbis (isooctyl mercaptopropionate), dibutyltinbis (isooctylthioate). A tin catalyst containing a sulfur atom, such as glycolate), is particularly preferred.

The amount of the urethanization catalyst added can be appropriately set by those skilled in the art, but from the viewpoint of reaction activity, 1 to 1000 ppm is preferable, and 10 to 100 ppm is more preferable with respect to 100 parts by weight of the polyoxyalkylene polymer (C). In this range, in addition to obtaining sufficient reaction activity, the obtained polyoxyalkylene polymer (A) retains good physical properties such as heat resistance, weather resistance, hydrolysis resistance, and storage stability. it can.

The urethanization reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the polyoxyalkylene polymer (C), the compound (H), and the urethanization catalyst, and the reaction system. In order to easily realize temperature control and addition of a urethanization catalyst, an organic solvent may be added.

The temperature of the urethanization reaction can be appropriately set by those skilled in the art, but is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. The reaction time may be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction between the polymers does not proceed. Specifically, the reaction time is preferably 15 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.

As yet another method for producing the polyoxyalkylene polymer (A), a silyl group reactive in one molecule and a mercaptan with respect to the polyoxyalkylene polymer (F) having an olefin group in the terminal structure. A method in which a compound (I) having a group is allowed to act to form a sulfide bond by adding a mercaptan group to an olefin group to introduce a reactive silyl group can also be applied. Also by this method, the polyoxyalkylene polymer (A) having a reactive silyl group can be produced.

Examples of the compound (I) having a reactive silyl group and a mercaptan group in one molecule include a mercaptan group capable of an addition reaction to an olefin group of the polyoxyalkylene polymer (F) and a reactive silyl group. The compound is not particularly limited as long as it is a compound contained in one molecule, but specific examples thereof include (3-mercaptopropyl) methyldimethoxysilane, (3-mercaptopropyl) trimethoxysilane, and (3-mercaptopropyl) methyldiethoxysilane. , (3-Mercaptopropyl) triethoxysilane, (mercaptomethyl) methyldimethoxysilane, (mercaptomethyl) trimethoxysilane, (mercaptomethyl) methyldiethoxysilane, (mercaptomethyl) triethoxysilane and the like.

The amount of the compound (I) having a reactive silyl group and a mercaptan group in one molecule may be appropriately determined in consideration of the amount of the olefin group contained in the polyoxyalkylene polymer (F). Specifically, the molar ratio of the mercaptan group of the compound (I) to the olefin group of the polyoxyalkylene polymer (F) is preferably 0.5 or more, more preferably 0.8 or more, and 0. 0.9 or more is more preferable. The upper limit of the amount of compound (I) used is not particularly limited, and the molar ratio is preferably 1 or less, but may exceed 1. When the molar ratio exceeds 1, the excess compound (I) may be removed by a treatment such as vacuum devolatilization after the addition reaction, or may be reacted with an unsaturated group-containing compound or the like to convert it into another compound. Alternatively, it may remain in the polyoxyalkylene polymer (A). The compound (I) remaining in the polyoxyalkylene polymer (A), or a derivative thereof, can act as a silane coupling agent.

The addition reaction of the mercaptan group to the olefin group may be carried out without using a radical initiator, but it is carried out in the presence of a radical initiator for the purpose of improving the reaction rate or the reaction rate. May be good. As such a radical initiator, conventionally known ones can be used. Specific examples thereof include, but are not limited to, an azo-based initiator and a peroxide-based initiator.

Among the known radical initiators, a catalyst having low activity with respect to the reactive silyl group is preferable, and from this viewpoint, 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis (2). Azo-based initiators such as -methylbutyronitrile) (V-59) and 2,2'-azobis (1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.

The amount of the radical initiator added can be appropriately set by those skilled in the art, but from the viewpoint of reaction activity, 0.01 to 10 parts by weight is preferable with respect to 100 parts by weight of the polyoxyalkylene polymer (F), and 0.1 to 1 part by weight. 10 parts by weight is more preferable. The radical initiator may be used in a state of being dissolved in an organic solvent.

The temperature of the addition reaction can be appropriately set by those skilled in the art, but is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. The reaction time may be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction between the polymers does not proceed. Specifically, the reaction time is preferably 15 minutes or more and 10 hours or less, and more preferably 30 minutes or more and 6 hours or less.

((Meta) acrylic acid ester polymer (B))
The curable composition of the present invention further contains a (meth) acrylic acid ester-based polymer (B) having a reactive silyl group.

The reactive silyl group contained in the (meth) acrylic acid ester polymer (B) has the following general formula (2):
−SiR ² _b Y _3-b (2)
It is represented by.

R ² represents an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Here, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The R ^2, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, tert- butyl group, n- hexyl, 2-ethylhexyl group, n- alkyl groups such as dodecyl group; Unsaturated hydrocarbon groups such as vinyl group, isopropenyl group and allyl group; cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, toluyl group and 1-naphthyl group; aralkyl group such as benzyl group and the like. .. It is preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group or a phenyl group, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. As R ² , only one type of group may be used, or two or more types of groups may be used in combination.

Y represents a hydroxyl group or a hydrolyzable group. Examples of Y include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like. The above-mentioned alkoxy group and the like may have a substituent. An alkoxy group is preferable, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, a methoxy group and an ethoxy group are further preferable, and a methoxy group is particularly preferable, because the hydrolyzability is mild and easy to handle. As Y, only one type of group may be used, or two or more types of groups may be used in combination.

B in the formula (2) is 0, 1 or 2. It is preferably 0 or 1. It is more preferably 1 in terms of the balance between the curability of the curable composition and the physical properties of the cured product, and more in that the curability of the composition and the resilience of the cured product can be further enhanced. It is preferably 0.

Examples of the reactive silyl group represented by the general formula (2) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, and a methyldi. Ethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, n-propyldimethoxysilyl group, n-hexyldimethoxysilyl group, phenyldimethoxysilyl group, phenyldiethoxysilyl group, methyldiisopropenoxysilyl group, methyldi Examples thereof include a phenoxysilyl group and a dimethylmethoxysilyl group. A methyldimethoxy group is more preferable from the viewpoint of achieving both storage stability and curability of the curable composition, and a trimethoxysilyl group can further enhance the curability of the composition and the resilience of the cured product. Is more preferable.

Further, the reactive silyl group of the polyoxyalkylene polymer (A) and the reactive silyl group of the (meth) acrylic acid ester polymer (B) may be the same or different.

In the present invention, the bond positions and the number of reactive silyl groups of the (meth) acrylic acid ester-based polymer (B) satisfy specific conditions. That is, in one molecule of the (meth) acrylic acid ester-based polymer (B), the average number of reactive silyl groups bonded to the ends of the polymer skeleton is 0.30 or more and 1.00 or less, and the polymer skeleton. The average number of reactive silyl groups bonded to the inside of the above is 0.01 or more and 0.20 or less. The average number of the former is the average number of reactive silyl groups bonded to the end of the polymer skeleton among the reactive silyl groups contained in one molecule of the polymer (B), and the average number of the latter is , The average number of reactive silyl groups bonded to the inside of the polymer skeleton among the reactive silyl groups contained in one molecule of the polymer (B). By using the (meth) acrylic acid ester-based polymer (B) satisfying these conditions in combination with the above-mentioned polyoxyalkylene-based polymer (A), the curable composition of the present invention has high strength and high strength after curing. It is possible to achieve both growth. Specifically, the numerical value of the average number can be calculated by the method described in the examples. In addition to the methods described in Examples, the numerical value of the average number can also be calculated from the results of GPC measurement and NMR measurement of the (meth) acrylic acid ester-based polymer (B).

Here, the reactive silyl group bonded to the terminal of the polymer skeleton is a reactive silyl group bonded to the terminal of the polymer skeleton formed by linking a plurality of monomer units. Point to that. Such a reactive silyl group attached to the terminal can be suitably formed, for example, by a method using a chain transfer agent described later, for example, without limitation. The (meth) acrylic acid ester-based polymer (B) having an average number of reactive silyl groups bonded to the ends of 1.00 or less in the present invention is, for example, a reactive silyl group with respect to one terminal of the polymer skeleton. It can be formed by adopting the method of introducing. The (meth) acrylic acid ester-based polymer (B) in the present invention is a polymer having a reactive silyl group at one end of the polymer skeleton but not having a reactive silyl group at the other end. Is preferable.

On the other hand, if a method in which reactive silyl groups are introduced into each of the two ends of the polymer skeleton is adopted, the average number of reactive silyl groups bonded to the ends in one molecule of the polymer is about 2. .. The (meth) acrylic acid ester-based polymer (B) in the present invention preferably does not contain a (meth) acrylic acid ester-based polymer having a reactive silyl group at each of the two terminals of such a polymer skeleton. ..

Further, the reactive silyl group bonded to the inside of the polymer skeleton is a plurality of monomer units constituting the polymer skeleton except for the monomer unit located at the end of the polymer skeleton described above. Refers to a reactive silyl group attached to either. Such a reactive silyl group may be described as being attached to the polymer as a side chain. Such an internally bonded reactive silyl group is not limited, but can be suitably formed by, for example, a method of copolymerizing a monomer having a reactive silyl group described later. In this case, the average number of reactive silyl groups bonded to the inside of the polymer skeleton in one polymer molecule can be adjusted by adjusting the amount of the monomer having the reactive silyl group used.

In one molecule of the (meth) acrylic acid ester-based polymer (B), the average number of reactive silyl groups bonded to the ends of the polymer skeleton is 0.30 or more and 1.00 or less, but the curability of the present invention Since the strength of the cured product of the composition can be further improved, it is preferably 0.70 or more and 1.00 or less, and more preferably 0.90 or more and 1.00 or less.

Further, in one molecule of the (meth) acrylic acid ester-based polymer (B), the average number of reactive silyl groups bonded to the inside of the polymer skeleton is 0.01 or more and 0.20 or less. The average number is preferably 0.03 or more and 0.15 or less, and more preferably 0.05 or more and 0.10 or less because the strength and elongation of the cured product of the curable composition of the present invention can be improved together. preferable.

Further, the average number of reactive silyl groups contained in one molecule of the (meth) acrylic acid ester-based polymer (B) (that is, the average number of reactive silyl groups bonded to the ends of the polymer skeleton described above, and the polymer. The total number of reactive silyl groups bonded to the inside of the skeleton) is limited to the range of 0.31 or more and 1.20 or less depending on the above-mentioned conditions, but is preferably 0.73 or more and 1.15 or less. , More preferably 0.95 or more and 1.10 or less.

The (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer (B) is not particularly limited, and various types can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , (Meta) tert-butyl acrylate, (meth) n-pentyl acrylate, (meth) n-hexyl acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n (meth) acrylate -Octyl, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) acrylate (3-trimethoxysilyl) propyl, (meth) acrylate (3-dimethoxymethylsilyl) propyl, (meth) acrylate (2-trimethoxysilyl) ethyl, (Meta) acrylic acid (2-dimethoxymethylsilyl) ethyl, (meth) acrylic acid trimethoxysilylmethyl, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid ethylene oxide adduct, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, ( Perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) ) Examples thereof include (meth) acrylic acid-based monomers such as 2-perfluorohexyl ethyl acrylate, 2-perfluorodecyl ethyl (meth) acrylate, and 2-perfluorohexadecyl ethyl (meth) acrylate.

Examples of the monomer unit other than the above include acrylic acids such as acrylic acid and methacrylic acid; amide groups such as N-methylolacrylamide and N-methylolmethacrylicamide, epoxy groups such as glycidylacrylate and glycidylmethacrylate, and diethylaminoethylacrylate. , Diethylaminoethyl methacrylate, etc., and monomers containing nitrogen-containing groups.

As the (meth) acrylic acid ester-based polymer (B), a polymer obtained by copolymerizing a (meth) acrylic acid ester-based monomer and a vinyl-based monomer copolymerizable therewith is used. You can also do it. The vinyl-based monomer is not particularly limited, and is, for example, a styrene-based monomer such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and a salt thereof; perfluoroethylene, perfluoropropylene, etc. Fluorine-containing vinyl-based monomers such as vinylidene fluoride; silicon-containing vinyl-based monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; Acids, monoalkyl esters of fumaric acids and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Nitrile group-containing vinyl-based monomers such as acrylonitrile and maleimide nitrile; amide group-containing vinyl-based monomers such as acrylamide and methacrylicamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnate Vinyl ester-based monomers such as; alkenyl-based monomers such as ethylene and propylene; conjugated diene-based monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. It is also possible to use a plurality of these as copolymerization components.

In the present invention, methyl methacrylate is preferably contained as a monomer constituting the main chain of the (meth) acrylic acid ester-based polymer (B), and the (meth) acrylic acid ester-based polymer (B) is used. The proportion of methyl methacrylate in all the constituent monomer units is preferably 35% by weight or more and 85% by weight or less. However, the weight of all monomer units includes only the weight of the monomer and does not include the weight of the chain transfer agent and the radical initiator. When the proportion of methyl methacrylate in the (meth) acrylic acid ester-based polymer (B) is within the above range, the strength of the cured product of the composition according to the present invention can be further improved. The proportion of methyl methacrylate is more preferably 60% by weight or more and 85% by weight or less, and more preferably 70% by weight or more and 85% by weight or less.

In the present invention, the ratio of the total of alkyl methacrylate to all the monomer units constituting the (meth) acrylic acid ester-based polymer (B) is preferably 70% by weight or more and 85% by weight or less. However, the alkyl of the alkyl methacrylate is an unsubstituted alkyl group having 1 to 4 carbon atoms (specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, tert). -Butyl group, etc.), and the weight of all monomer units includes only the weight of the monomer and does not include the weight of the chain transfer agent and the radical initiator. When the proportion of alkyl methacrylate in the (meth) acrylic acid ester-based polymer (B) is within the above range, the strength of the cured product of the composition according to the present invention can be further improved. The ratio of the alkyl methacrylate is more preferably 75% by weight or more and 85% by weight or less.

The monomer composition of the (meth) acrylic acid ester-based polymer (B) is generally selected by those skilled in the art depending on the application and purpose, but in applications that require strength such as an adhesive, it is used. The (meth) acrylic acid ester polymer (B) preferably has a relatively high glass transition temperature (Tg), preferably 0 ° C. or higher and 200 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower. Is good. Tg is obtained from the following Fox formula.

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

The method for synthesizing the (meth) acrylic acid ester-based polymer (B) is not particularly limited, and examples thereof include known methods. The radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of control of the polymerization reaction.

The radical polymerization method can be roughly divided into a "free radical polymerization method" and a "living radical polymerization method". The "free radical polymerization method" is a method for polymerizing a monomer using an azo compound, a peroxide or the like as a polymerization initiator, and is a simple polymerization method. According to the "free radical polymerization method", it is also possible to obtain a polymer having a functional group at the end of the polymer skeleton by using a chain transfer agent having a specific functional group. On the other hand, in the "living radical polymerization method", the polymer growth end grows under specific reaction conditions without causing a side reaction such as a termination reaction. According to the "living radical polymerization method", a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained, and a constituent unit amount derived from a monomer having a specific functional group. It is possible to introduce the body unit at almost any position on the polymer. Details of these polymerization methods are disclosed in paragraphs [0086] to [0094] of International Publication No. 2012/20560 and [0061] to [0068] of JP-A-2014-114434.

As a polymerization method other than the above, a method for obtaining an acrylic polymer by using a metallocene catalyst as shown in JP-A-2001-040037 and a thiol compound having at least one reactive silyl group in the molecule. Alternatively, a vinyl-based monomer as shown in JP-A-57-502171, JP-A-59-006207, and JP-A-60-511992 is used in a stirring tank type reactor. It is also possible to use a high-temperature continuous polymerization method or the like in which continuous polymerization is carried out using.

The method for introducing the reactive silyl group into the (meth) acrylic acid ester polymer is not particularly limited, and for example, the following method can be used.
(Iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silyl group together with the above-mentioned monomer. Using this method, reactive silyl groups tend to be randomly introduced inside the polymer backbone.
(V) A method for polymerizing a (meth) acrylic acid ester-based polymer using a mercaptosilane compound having a reactive silyl group as a chain transfer agent. Using this method, reactive silyl groups can be introduced at the ends of the polymer backbone.
(Vi) A method in which a compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then the reactive silyl group and the compound having a functional group that reacts with the V group are reacted. Specifically, a method of copolymerizing 2-hydroxyethyl acrylate and then reacting with an isocyanate silane having a reactive silyl group, or a method of copolymerizing glycidyl acrylate and then reacting with an aminosilane compound having a reactive silyl group. An example of how to make it.
(Vii) A method for introducing a reactive silyl group by modifying the terminal functional group of the (meth) acrylic acid ester-based polymer synthesized by the living radical polymerization method. In the living radical polymerization method, a functional group can be easily introduced at the end of the polymer skeleton, and by modifying this, a reactive silyl group can be introduced at the end of the polymer skeleton.

Examples of the silicon compound that can be used to introduce a reactive silyl group into the (meth) acrylic acid ester-based polymer by the above method include the following compounds. Examples of the compound having a polymerizable unsaturated group and a reactive silyl group used in the method (iv) include 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (dimethoxymethylsilyl) propyl (meth) acrylate. , (Meta) Acrylic Acid 3- (Triethoxysilyl) Propyl, (Meta) Acrylic Acid (Trimethoxysilyl) Methyl, (Meta) Acrylic Acid (Dimethoxymethylsilyl) Methyl, (Meta) Acrylic Acid (Triethoxysilyl) Methyl , (Meta) acrylic acid (diethoxymethylsilyl) methyl, (meth) acrylic acid 3-((methoxymethyl) dimethoxysilyl) propyl and the like. From the viewpoint of availability, 3-trimethoxysilylpropyl (meth) acrylate and 3- (dimethoxymethylsilyl) propyl (meth) acrylate are particularly preferable.

Examples of the mercaptosilane compound having a reactive silyl group used in the method (v) include (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) dimethoxymethylsilane, (3-mercaptopropyl) triethoxysilane, and (3. Examples thereof include mercaptomethyl) trimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) triethoxysilane.

Examples of the compound having a functional group that reacts with the reactive silyl group and the V group used in the method (vi) include (3-isocyanuppropyl) trimethoxysilane, (3-isocyanvopropyl) dimethoxymethylsilane, and (3-isocyanabylpropyl). ) Silanesilane compounds such as (Isocyanicmethyl) trimethoxysilane, (Isocyanicmethyl) triethoxysilane, (Isocyanicmethyl) dimethoxymethylsilane, (Isocyanicmethyl) diethoxymethylsilane; (3-glycidoxypropyl) ) Trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) dimethoxymethylsilane, (glycidoxymethyl) trimethoxysilane, (glycidoxymethyl) triethoxysilane, ( Epoxysilane compounds such as glycidoxymethyl) dimethoxymethylsilane, (glycidoxymethyl) diethoxymethylsilane; (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, (3-aminopropyl) ) Dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (aminomethyl) triethoxysilane, (aminomethyl) dimethoxymethylsilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-cyclohexylamino) methyldiethoxymethyl Silane, (N-phenylaminomethyl) trimethoxysilane, (N- (2-aminoethyl) aminomethyl) trimethoxysilane, (N- (2-aminoethyl) -3-aminopropyl) trimethoxysilane, etc. Examples include aminosilane compounds.

In the above method (vii), any modification reaction can be used. For example, a method using a compound having a functional group and a reactive silicon group capable of reacting with the terminally reactive group obtained by polymerization, or a terminal reactivity is used. A method of introducing a double bond at the end of the polymer skeleton using a compound having a functional group capable of reacting with a group and a double bond, and introducing a reactive silyl group into the terminal by hydrosilylation or the like can be used.

In addition, these methods may be used in arbitrary combination. For example, by combining the method (vi) and the method (v), a (meth) acrylic acid ester-based polymer having a reactive silyl group both at the end and inside of the polymer skeleton can be obtained.

The number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is not particularly limited, but the polystyrene-equivalent molecular weight measured by GPC is preferably 500 to 100,000, more preferably 1,000 to 10,000, and 1 , 200-3,000 are particularly preferred. When the number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is within the above range, it is easy to form a cured product showing sufficient strength and elongation, and a desirable viscosity is achieved from the viewpoint of workability. Cheap.

Examples of the method for blending the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer are JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763. It is proposed in the publication. In addition, a method of polymerizing a (meth) acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silyl group can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-60-228516, JP-A-60-228517 and the like. The polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) of the present invention can also be blended by the same method, but are not limited thereto.

The weight ratio of the polyoxyalkylene polymer (A): (meth) acrylic acid ester polymer (B) in the curable composition of the present invention is not particularly limited, but 90: 10 to 40:60 is preferable, and 75 : 25 to 50:50 is more preferable, 75:25 to 55:45 is even more preferable, and 70:30 to 60:40 is particularly preferable. When the weight ratio of both polymers is within the above range, the curable composition of the present invention tends to achieve a desired viscosity from the viewpoint of workability, and tends to achieve high strength and high elongation after curing. Further, the polyoxyalkylene polymer (A): (meth) acrylic acid ester polymer (B) is preferably compatible with each other. By selecting the type of monomer constituting each polymer and the ratio thereof, both polymers can be configured to be compatible with each other. As the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) of the present invention, only one kind may be used, or two or more kinds may be used in combination.

(Silanol condensation catalyst)
The curable composition of the present invention hydrolyzes and dehydrates and condenses the reactive silyl groups of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B), that is, a curing reaction. For the purpose of facilitating, it is preferable to contain a silanol condensation catalyst.

As the silanol condensation catalyst, conventionally known ones can be used, and specifically, organotin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like can be used.

Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis (butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin oxide and silicate compounds. Reactant with, dibutyltin oxide and phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis (ethylmalate), dioctyltin bis (octylmaleate), dioctyltin bis (acetylacetate) Nart), a reaction product of dioctyl tin oxide and a silicate compound, and the like. Due to the growing interest in the environment in recent years, dioctyltin compounds are preferred.

Specific examples of the metal carboxylate salt include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, and the like. As the carboxylic acid group, the following carboxylic acids and various metals can be combined.

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

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of the alkoxy metal include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate. Examples thereof include aluminum compounds such as, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators and photobase generators can also be used.

The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, by using the amine compound and the carboxylic acid in combination, the effect of improving the reactivity may be obtained.

The amount of the silanol condensation catalyst to be blended is preferably 0.001 to 20 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). Further, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable. If the blending amount of the silanol condensation catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, if the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the reaction rate is too fast, so that the usable time of the composition is shortened, which tends to deteriorate workability and storage stability. Further, some silanol condensation catalysts may exude to the surface of the cured product or contaminate the surface of the cured product after the curable composition is cured. In such a case, by setting the amount of the silanol condensation catalyst used to 0.01 to 3.0 parts by weight, the surface condition of the cured product can be kept good while ensuring the curability.

(Other additives)
In the curable composition of the present invention, as other additives, a silicon compound, an adhesive-imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an antioxidant, an antioxidant, a light stabilizer, and ultraviolet rays. Even if absorbents, property modifiers, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen curable substances, surface improvers, epoxy resins, other resins, flame retardants, and foaming agents are added. good. In addition, various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include curability regulators, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, fungicides and the like. Be done.

<Filler>
Various fillers can be added to the composition of the present invention. As fillers, heavy calcium carbonate, collagen carbonate, magnesium carbonate, silica soil, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, molten silica, silicic acid anhydride, hydrous silicic acid, Examples thereof include carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament. The above filler may be used alone or in combination of two or more.

The amount of the filler used is preferably 1 to 300 parts by weight, particularly 10 to 300 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). 250 parts by weight is preferable.

An organic balloon or an inorganic balloon may be added for the purpose of reducing the weight (lower specific gravity) of the composition. The balloon is a spherical filler with a hollow inside, and the material of this balloon is an inorganic material such as glass, silas, and silica, and an organic material such as phenol resin, urea resin, polystyrene, and saran. Materials can be mentioned. Only one type of the balloon may be used, or two or more types may be mixed and used.

The amount of the balloon used is preferably 0.1 to 100 parts by weight, particularly 1 part by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). ~ 20 parts by weight is preferable.

<Adhesive imparting agent>
An adhesiveness-imparting agent can be added to the composition of the present invention. As the adhesiveness-imparting agent, a silane coupling agent and a reaction product of the silane coupling agent can be added.

Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl). )-3-Aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane and other amino group-containing silanes; (3-isocyanatepropyl) trimethoxysilane , 3- (Isocyanatepropyl) triethoxysilane, (3-Isocyanatepropyl) methyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane and other isocyanate group-containing silanes; (3-mercaptopropyl) Mercapt group-containing silanes such as trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) methyldimethoxysilane; (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-) Examples thereof include epoxy group-containing silanes such as (epoxycyclohexyl) ethyltrimethoxysilane. Further, reactants of various silane coupling agents can also be used. The adhesive-imparting agent may be used alone or in combination of two or more.

The amount of the adhesive-imparting agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). , Especially preferably 0.5 to 10 parts by weight.

<Plasticizer>
A plasticizer can be added to the composition of the present invention. Specific examples of the plasticizer include phthalate compounds such as dibutylphthalate, diisononylphthalate (DINP), diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate (DIDP), and butylbenzylphthalate; bis (2-ethylhexyl). ) A terephthalate compound such as -1,4-benzenedicarboxylate; a non-phthalate compound such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliper polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinolate; alkyl sulfonic acid phenyl ester; phosphoric acid ester compound; trimellitic acid ester compound; chlorination Paraffin; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxy plasticants such as benzyl epoxidate stearate, and the like can be mentioned.

Moreover, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include a vinyl polymer; a polyester plasticizer; a polyether polyol such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and the hydroxy group of these polyether polyols is an ester group or an ether group. Polyesters such as derivatives converted into the above; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like can be mentioned.

The amount of the plasticizer used is preferably 5 to 150 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). By weight is more preferred, especially 20 to 100 parts by weight. 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 plasticizer may be used alone or in combination of two or more.

<Solvent, diluent>
Solvents or diluents can be added to the compositions of the present invention. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers 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, due to the problem of air pollution when the composition is used indoors. .. The above solvent or diluent may be used alone or in combination of two or more.

<Sauce preventive agent>
If necessary, a sagging inhibitor may be added to the composition of the present invention in order to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sauce agents may be used alone or in combination of two or more.

The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B).

<Antioxidant>
Antioxidants (anti-aging agents) can be used in the compositions of the present invention. The use of antioxidants can enhance the weather resistance of the cured product. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols. 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, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). In particular, 0.2 to 5 parts by weight is preferable.

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

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). In particular, 0.2 to 5 parts by weight is preferable.

<UV absorber>
An ultraviolet absorber can be used in the composition of the present invention. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, but benzotriazole-based compounds are particularly preferable, and commercially available names such as tinubin P, tinubin 213, tinubin 234 and tinubin 326, Examples thereof include chinubin 327, chinubin 328, chinubin 329, and chinubin 571 (all manufactured by BASF).

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). In particular, 0.2 to 5 parts by weight is preferable.

<Physical property adjuster>
If necessary, a physical property adjusting agent for adjusting the tensile properties of the produced cured product may be added to the curable composition of the present invention. The physical property adjusting agent is not particularly limited, and for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane and phenyltrimethoxysilane. Arylalkoxysilanes such as: dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, alkylisopropenoxysilane such as γ-glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, tris (triethyl) Examples thereof include trialkylsilylborates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property adjusting agent, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be decreased to achieve elongation at break. The physical property adjusting agent may be used alone or in combination of two or more.

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 aggravating the stickiness of the surface of the cured product. In particular, compounds that produce trimethylsilanol are preferred. Compounds that produce compounds having a monovalent silanol group in the molecule by hydrolysis are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and are silane monomono by hydrolysis. Silicon compounds that produce oars can be mentioned.

The amount of the physical property adjusting agent used is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). In particular, 0.5 to 5 parts by weight is preferable.

<Adhesive resin>
A tackifier resin can be added to the composition of the present invention for the purpose of enhancing the adhesiveness and adhesion to the base material, or if necessary. The tackifying resin is not particularly limited, and a commonly used resin can be used.

Specific examples include terpen-based resins, aromatic-modified terpen resins, hydrocarbon-modified terpen resins, terpen-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, kumaron inden resins, and rosin-based resins. Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogen additives, petroleum resins (eg, C5 hydrocarbon resins, C9). Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin, etc. can be mentioned. These may be used alone or in combination of two or more.

The amount of the tackifier resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is more preferably parts by weight, and even more preferably 5 to 30 parts. If it is less than 2 parts by weight, it is difficult to obtain the effect of adhesion and adhesion to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition becomes too high and handling may be difficult.

<Compounds containing epoxy groups>
In the composition of the present invention, a compound containing an epoxy group can be used. The use of a compound having an epoxy group can enhance the resilience of the cured product. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in 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. , Epoxy butyl steerate and the like. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). ..

<Photocurable substance>
A photocurable substance can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many compounds of this type are known, such as organic monomers, oligomers, resins, and compositions containing them, and typical ones include one or several acrylic or methacrylic unsaturated groups. An unsaturated acrylic compound, vinyl polysilicate dermatates, an azide resin, or the like, which is a monomer, an oligomer, or a mixture thereof, can be used.

The photocurable substance is 0.1 to 20 parts by weight, preferably 0.5 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is preferably used in the range of 10 parts by weight, and if it is 0.1 parts by weight or less, there is no effect of increasing weather resistance, and if it is 20 parts by weight or more, the cured product becomes too hard and tends to crack.

<Oxygen curable substance>
An oxygen-curable substance can be used in the composition of the present invention. An example of an unsaturated compound that can react with oxygen in the air is an oxygen-curable substance that reacts with oxygen in the air to form a cured film near the surface of the cured product, which causes 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-curable substance include drying oils such as drilling oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with the drying oils. , Silicon resin; polymers of 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Examples include liquid polymers. These may be used alone or in combination of two or more.

The amount of the oxygen-curable substance used is in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is best to use, more preferably 0.5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product 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.

<Epoxy resin>
An epoxy resin can be used in combination with the composition of the present invention. The composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly an adhesive for outer wall tiles. Examples of the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.

Epoxy resin: The ratio of "total of polyoxyalkylene polymer (A) and (meth) acrylic acid ester polymer (B)" is (A) + (B) / epoxy resin = 100 by weight. It is in the range of / 1 to 1/100. When the ratio of (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, and (A) + (B) / epoxy resin. If the ratio of the above is more than 100/1, the strength of the cured product becomes insufficient.

When an epoxy resin is added, a curing agent that cures the epoxy resin can be used in combination with the composition of the present invention. The epoxy resin curing agent that can be used is not particularly limited, and a generally used epoxy resin curing agent can be used.

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.

<< Preparation of curable composition >>
The curable composition of the present invention can be prepared as a one-component type in which all the compounding components are compounded and sealed in advance and cured by the moisture in the air after construction, and separately as a curing agent, a silanol condensation catalyst, It is also possible to prepare a two-component type in which components such as a filler, a plasticizer, and water are blended and the compounding material and the resin 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 components are pre-blended. Therefore, the moist-containing compounding components are either dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding kneading. Is preferable. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxy Storage stability is further improved by adding an alkoxysilane compound such as silane.

The amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). On the other hand, the range of 0.1 to 20 parts by weight is preferable, and the range of 0.5 to 10 parts by weight is more preferable.

<Use>
The curable composition of the present invention is an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a coating film waterproofing material, a molding agent, a vibration-proofing material, a vibration-damping material, and a soundproofing material. , Can be used as foaming material, paint, spraying material. The cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, and therefore can be suitably used as a sealing material or an adhesive.

Further, the curable composition of the present invention includes electric / electronic component materials such as a solar cell backside sealing material, electrical / electronic components such as an insulating coating material for electric wires / cables, an electrical insulating material for an apparatus, and an acoustic insulating material. Elastic Adhesives, Binders, Contact Adhesives, Spray Sealing Materials, Crack Repairing Materials, Tiling Adhesives, Asphalt Waterproof Adhesives, Powder Paints, Casting Materials, Medical Rubber Materials, Medical Adhesives , Medical adhesive sheets, medical equipment sealing materials, dental impression materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, conductive materials for electromagnetic wave shielding, Thermal conductive material, hot melt material, potting agent for electrical and electronic use, film, gasket, concrete reinforcing material, adhesive for temporary fixing, various molding materials, and rust prevention of wire-reinforced glass and laminated glass end face (cut part) Used for various purposes such as waterproof sealing materials, large vehicle parts such as automobile parts, trucks and buses, train vehicle parts, aircraft parts, marine parts, electrical parts, liquid sealants used in various mechanical parts, etc. It is possible. Taking an automobile as an example, it can be used in a wide variety of ways such as plastic covers, trims, flanges, bumpers, window mountings, interior members, and adhesive mounting of exterior parts. In addition, it can be used alone or with the help of primers as it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., and can be used as various types of sealing and adhesive compositions. .. The curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, leather, textiles, fabrics, paper, board and rubber bonding adhesives, reactive post-bridge pressure sensitive adhesives, direct It can also be used as a glazing sealant, a multi-layer glass sealant, an SSG method sealant, a building working joint sealant, a civil engineering material, and a bridge material. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid transfer system: Tosoh HLC-8220GPC
Column: Tosoh TSKgel SuperH series Solvent: THF
Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C

(Method for calculating the average number of reactive silyl groups bonded to the end or inside of the polymer skeleton in one molecule of (meth) acrylic acid ester polymer)
It was calculated by the concentration of reactive silyl groups in the polymer calculated from the amounts of the reactive silyl group-containing monomer and the reactive silyl group-containing chain transfer agent, and the number average molecular weight of the polymer measured by GPC. Specifically, it was calculated using the following formula. In the following, "the average number of reactive silyl groups bonded to the ends of the polymer skeleton in one molecule of the (meth) acrylic acid ester-based polymer" and "the polymer in one molecule of the (meth) acrylic acid ester-based polymer". The "average number of reactive silyl groups bonded to the inside of the skeleton" is referred to as "the number of terminally bonded silyl groups" and "the number of internally bonded silyl groups", respectively.
Number of end-bonded silyl groups = (number average molecular weight of polymer / total number of solids during polymer synthesis) x [(total number of parts used for each reactive silyl group-containing chain transfer agent / molecular weight of the chain transfer agent)]
Number of internally bonded silyl groups = (number average molecular weight of polymer / total number of solids during polymer synthesis) × [(total number of copies of each reactive silyl group-containing monomer / molecular weight of the monomer)]

(Synthesis Example 1-1) Polymer (C-1)
Starting with polyoxypropylene triol having a number average molecular weight of about 4,500, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst until the following molecular weight is reached, and a branched type having a number average molecular weight of about 26,000. A hydroxyl group-terminated polyoxypropylene (C-1) was obtained.

(Synthesis Example 1-2) Polymer (C-2)
Starting with polyoxypropylene diol having a number average molecular weight of about 4,500, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst until the following molecular weight is reached, and a straight chain having a number average molecular weight of about 28,000. A type hydroxyl group terminal polyoxypropylene (C-2) was obtained.

(Synthesis Example 1-3) Polymer (C-3)
Starting with polyoxypropylene triol having a number average molecular weight of about 4,500, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst until the following molecular weight is reached, and a branched type having a number average molecular weight of about 20,000. A hydroxyl group-terminated polyoxypropylene (C-3) was obtained.

(Synthesis Example 1-4) Polymer (C-4)
Starting with polyoxypropylene triol having a number average molecular weight of about 4,500, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst until the following molecular weight is reached, and a branched type having a number average molecular weight of about 16,000. A hydroxyl group-terminated polyoxypropylene (C-4) was obtained.

(Synthesis Example 2-1) Polymer (A-1)
To the hydroxyl group of the polymer (C-1), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 1.5 parts by weight of (methoxymethyl) dimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene. By reacting at 90 ° C. for 2 hours, a branched polyoxypropylene (A-1) having a number average molecular weight of 26,000 and having a (methoxymethyl) dimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-2) Polymer (A-2)
1.0 equivalent of a methanol solution of sodium methoxydo was added to the hydroxyl group of the polymer (C-1), methanol was distilled off at 140 ° C., and 1.0 equivalent of allyl glycidyl ether was added at 140 ° C. The reaction was carried out for 2 hours to introduce a structure containing an allyl group and a hydroxyl group, and 1.5 equivalents of 3-chloro-1-propene was further added to convert the hydroxyl group into an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 3.0 parts by weight of (methoxymethyl) dimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene. By reacting at 90 ° C. for 2 hours, a branched polyoxypropylene (A-2) having a number average molecular weight of 26,000 and having a (methoxymethyl) dimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-3) Polymer (A-3)
To the hydroxyl group of the polymer (C-1), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 1.3 parts by weight of methyl dimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the temperature was 90 ° C. By reacting with (A-3) for 2 hours, a branched polyoxypropylene (A-3) having a number average molecular weight of 26,000 and having a methyldimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-4) Polymer (A-4)
To the hydroxyl group of the polymer (C-3), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (isopropyl alcohol solution of 3% by mass in terms of platinum) and 1.5 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the temperature was 90 ° C. By reacting with the above for 2 hours, a branched polyoxypropylene (A-4) having a number average molecular weight of 20,000 and having a methyldimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-5) Polymer (A-5)
To the hydroxyl group of the polymer (C-1), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 50 ppm by weight of a platinum divinyldisiloxane complex (isopropyl alcohol solution of 3% by mass in terms of platinum) and 1.4 parts by weight of trimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the temperature was 90 ° C. By reacting with the above for 2 hours, a branched polyoxypropylene (A-5) having a number average molecular weight of 26,000 and having a trimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-6) Polymer (A-6)
To the hydroxyl group of the polymer (C-4), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 2.4 parts by weight of (methoxymethyl) dimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene. By reacting at 90 ° C. for 2 hours, a branched polyoxypropylene (A-6) having a number average molecular weight of 16,000 and having a (methoxymethyl) dimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-7) Polymer (A-7)
To the hydroxyl group of the polymer (C-4), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 2.4 parts by weight of methyl dimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the temperature was 90 ° C. By reacting with the above for 2 hours, a branched polyoxypropylene (A-7) having a number average molecular weight of 16,000 and having a methyldimethoxysilyl group at the terminal was obtained.

(Synthesis Example 2-8) Polymer (A-8)
To the hydroxyl group of the polymer (C-2), 1.2 equivalents of a methanol solution of sodium methoxide was added, methanol was distilled off at 140 ° C., and 1.6 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (isopropyl alcohol solution of 3% by mass in terms of platinum) and 0.95 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene to 90 ° C. A linear polyoxypropylene (A-8) having a number average molecular weight of 28,000 and having a methyldimethoxysilyl group at the terminal was obtained by reacting with.

(Synthesis Example 3-1)
53.7 parts by weight of isobutyl alcohol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 ° C. under a nitrogen atmosphere. There, 77.8 parts by weight of methyl methacrylate, 6.7 parts by weight of butyl acrylate, 15.0 parts by weight of stearyl methacrylate, 0.5 parts by weight of 3- (methyldimethoxysilylpropyl) methacrylate, (3-mercapto). A mixed solution of 10.0 parts by weight of propyl) methyldimethoxysilane and 0.35 parts by weight of 2,2'-azobis (2-methylbutyronitrile) in 19.8 parts by weight of isobutyl alcohol was added over 3.5 hours. Dropped. Further polymerizing at 105 ° C. for 2 hours, an isobutyl alcohol solution (solid content 60 weight) of the (meth) acrylic acid ester polymer (B-1) having a number average molecular weight of 1,900 and a weight average molecular weight of 3,400. %) Was obtained. In the polymer (B-1), the number of terminally bonded silyl groups was 0.95 and the number of internally bonded silyl groups was 0.04.

(Synthesis Example 3-2-3-10)
In the same procedure as in Synthesis Example 3-1 using various monomers, chain transfer agents, radical initiators, and solvents according to each polymerization formulation shown in Table 1, (meth) acrylic acid ester-based polymer (B-2). )-(B-11) in isobutyl alcohol solution was obtained. For each of the obtained polymers (B), the number of terminally bonded silyl groups, the number of internally bonded silyl groups, the number average molecular weight, the weight average molecular weight, and the solid content concentration are shown in Table 1.

(Synthesis Example 4-1)
The solid content ratio (mass ratio) of the polymer (A-1) obtained in Synthesis Example 2-1 and the isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 3-1 was 70 /. It was mixed at 30. The obtained mixture was heated to 110 ° C. using a rotary evaporator, and isobutyl alcohol was distilled off under reduced pressure under reduced pressure conditions. The polymer (A-1) / polymer (B) had a solid content concentration of 99% or more. A polymer mixture having a mass ratio of -1) of 70/30 was obtained. The viscosity of this polymer mixture at 23 ° C. was 85 Pa · s.

(Synthesis Example 4-2-4-18)
A polymer mixture was obtained from the polymer (A) and the polymer (B) according to each polymer type and mixture composition shown in Table 2 in the same procedure as in Synthesis Example 4-1. The viscosities of these polymer mixtures at 23 ° C. are shown in Table 2.

<Evaluation method of composition physical properties>
According to each composition shown in Tables 3 to 5, the polymer mixture obtained in each synthesis example and the filler and the anti-sagging agent among the various additives shown below are mixed and sufficiently mixed, and then three paint rolls are used. The main agent was prepared by dispersing the mixture three times. Then, a dehydrating agent, an adhesive-imparting agent, and a silanol condensation catalyst were added and sufficiently mixed, and the mixture was uniformly kneaded and defoamed using a rotation / revolution mixer to prepare each curable composition. Using each of the prepared curable compositions, various test specimens were prepared in a constant temperature and humidity atmosphere at 23 ° C. and a relative humidity of 50%, and various evaluations were performed.

(Various additives used in each Example and Comparative Example relating to the evaluation of the physical properties of the composition)
The following additives were used in the evaluation of the physical properties of the compositions of all Examples and Comparative Examples. The blending amount is the number of parts by weight with respect to 100 parts by weight of each polymer mixture as the base polymer.
filler:
(i) Fatty acid-treated precipitated calcium carbonate (Shirashinka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 50 parts by weight
(ii) Heavy calcium carbonate (Whiten SB red, manufactured by Shiraishi Calcium Co., Ltd.), 50 parts by weight anti-sagging agent: fatty acid amide wax (Disparon # 6500, Kusumoto Kasei Co., Ltd.), 0.5 parts by weight dehydrating agent : Vinyl trimethoxysilane (A-171, manufactured by Momentive Co., Ltd.), 3 parts by weight adhesive imparting agent: 3- (N-2-aminoethylamino) propyltrimethoxysilane (A-1120, manufactured by Momentive Co., Ltd.) ), 3 parts by weight silanol condensation catalyst: Any one of the following (see and amount added in each table)
(iii) 50% phenylguanidine solution (50% by weight solution of N-butylbenzenesulfonamide, manufactured by Nippon Carbide Co., Ltd.)
(iv) Dioctyl tin dilaurate (U-810, manufactured by Nitto Kasei Co., Ltd.)
(v) Dibutyltin bis (acetate acetate) (U-220H, manufactured by Nitto Kasei Co., Ltd.)

(Evaluation)
The curability and dumbbell physical properties of the prepared curable composition were measured by the following methods. The results are also shown in Tables 3 to 5.

(Curable)
The curable composition was filled in a mold having a thickness of about 5 mm using a spatula at 23 ° C. and a relative humidity of 50%, and the time when the surface was flattened was defined as the curing start time. The surface was touched with a spatula, and the curability was measured by setting the time until the composition did not adhere to the spatula as the skinning time.

(Dumbbell physical properties)
The curable composition was packed into a 3 mm thick sheet-like formwork at 23 ° C. and 50% relative humidity. After curing at 23 ° C. and a relative humidity of 50% for 3 days, it was cured in a dryer at 50 ° C. for 4 days to obtain a sheet-like cured product. The obtained cured product was punched into a No. 3 dumbbell mold according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23 ° C. and 50% relative humidity, and 50% elongation stress, 100% elongation stress, and fracture stress were performed. , And elongation at break was measured.

From the results shown in Table 3, the number of terminally bonded silyl groups is 0.30 or more and 1.00 or less and the number of internally bonded silyl groups is 0, with respect to the polyoxyalkylene polymer (A) having a reactive silyl group. The cured product of the composition (each example) containing the polymer mixture obtained by mixing the (meth) acrylic acid ester-based polymer (B) of 01 or more and 0.20 or less is based on the same polymer (A). A cured product of a composition (Comparative Example 1-1) containing a polymer mixture containing a (meth) acrylic acid ester-based polymer having 0 internally bonded silyl groups, or an internally bonded silyl group number exceeding 0.20. It can be seen that both the stress at break and the elongation at break are higher than those of the cured product of the composition (Comparative Examples 1-2 to 1-3) containing the polymer mixture mixed with the (meth) acrylic acid ester-based polymer. .. Further, a polymer mixture obtained by mixing a (meth) acrylic acid ester-based polymer having an internally bonded silyl group number of 0.01 or more and 0.20 or less but an end-bonded silyl group number of not 0.30 or more and 1.00 or less. It can be seen that the cured product of the composition containing (Comparative Example 1-4) is significantly inferior in stress at break. Further, a cured product of a composition (Comparative Example 1-5) containing a polymer mixture obtained by mixing a (meth) acrylic acid ester-based polymer having a large number of internally bonded silyl groups of 1.02 and 0 terminal-bonded silyl groups is also available. Compared with the composition (Example 1-2) containing a polymer mixture in which the (meth) acrylic acid ester-based polymer (B) having the same total number of internally bonded silyl groups and terminally bonded silyl groups is mixed. It can be seen that the stress at break and the elongation at break are both significantly inferior.

The results shown in Table 4 are the results using a polymer mixture of the polymer (A) and the polymer (B) in a combination not included in Table 3, but again, they have a reactive silyl group. A (meth) acrylic acid ester having a terminal-bonded silyl group number of 0.30 or more and 1.00 or less and an internally bonded silyl group number of 0.01 or more and 0.20 or less with respect to the polyoxyalkylene polymer (A). The cured product of the composition (each example) containing the polymer mixture mixed with the system polymer (B) is a polymer mixed with a (meth) acrylic acid ester-based polymer having an internally bonded silyl group number of more than 0.20. It can be seen that both the breaking stress and the breaking elongation are higher than those of the cured product of the composition containing the mixture (Comparative Example 2-1).

In particular, in each of the examples and comparative examples of Tables 3 and 4, those having a branched-chain polymer skeleton are used as the polyoxyalkylene polymer, but in each example, the number of silyl groups is small (meth). ) Compared with the comparative example in which the acrylic acid ester polymer is used, the stress at break is improved. The fact that the stress at break is improved despite the small number of silyl groups at the condensation point is a characteristic effect in these examples.

Table 5 shows the results when a polymer having a linear polymer skeleton was used as the polyoxyalkylene polymer. As a result, the number of terminally bonded silyl groups is 0.30 or more and 1.00 or less and the number of internally bonded silyl groups is 0.01 or more and 0.20 with respect to the polyoxyalkylene polymer (A) having a reactive silyl group. The cured product of the composition (Example 3-1) containing the polymer mixture obtained by mixing the (meth) acrylic acid ester-based polymer (B) below has the number of internally bonded silyl groups with respect to the same polymer (A). Compared with the cured product of the composition (Comparative Example 3-1) containing a polymer mixture containing a (meth) acrylic acid ester-based polymer having a value of more than 0.20, the stress at break was slightly lower, but at break. It can be seen that the growth has improved significantly. From this, the tendency of the cured physical properties is different between the case where the polymer skeleton of the polyoxyalkylene polymer has a branched chain shape shown in Tables 3 and 4 and the case where the polymer skeleton has a linear shape shown in Table 5. It can be seen that it is more desirable that the polymer skeleton of the polyoxyalkylene polymer has a branched chain shape in that both the stress at break and the elongation at break are improved.

Further, in any of Tables 3 to 5, it can be seen from the results of the skin-covering time measurement as the curability test that the curable composition satisfying the requirements of the present invention has sufficient curability. ..

From the above results, the number of terminally bonded silyl groups is 0.30 or more and 1.00 or less and the number of internally bonded silyl groups is 0.01 or more and 0 with respect to the polyoxyalkylene polymer (A) having a reactive silyl group. A composition containing a polymer mixture containing a (meth) acrylic acid ester-based polymer (B) of .20 or less can be suitably used as a curable composition showing high breaking stress and breaking elongation after curing. I understand.

Claims (8)

The following general 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 represents a hydroxyl group or a hydrolyzable group. A is 0, 1 or 2. R ¹ or X. When there are a plurality of polyoxyalkylene-based polymers (A) having a reactive silyl group represented by (they may be the same or different), and the following general formula (2):
−SiR ² _b Y _3-b (2)
(In the formula, R ² represents an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. B is 0, 1 or 2. Multiple R ² or Y. When present, they include a (meth) acrylic acid ester-based polymer (B), which has a reactive silyl group represented by (which may be the same or different).
The average number of reactive silyl groups bonded to the ends of the polymer skeleton in one molecule of the (meth) acrylic acid ester-based polymer (B) is 0.30 or more and 1.00 or less, and the (meth) acrylic acid ester. A curable composition in which the average number of reactive silyl groups bonded to the inside of the polymer skeleton in one molecule of the system polymer (B) is 0.01 or more and 0.20 or less. The curability according to claim 1, wherein the average number of reactive silyl groups bonded to the inside of the polymer skeleton in one molecule of the (meth) acrylic acid ester polymer (B) is 0.03 or more and 0.15 or less. Composition. The method according to claim 1 or 2, wherein the average number of reactive silyl groups bonded to the ends of the polymer skeleton in one molecule of the (meth) acrylic acid ester polymer (B) is 0.90 or more and 1.00 or less. Curable composition. The total proportion of alkyl methacrylate in the constituent monomer units of the (meth) acrylic acid ester-based polymer (B) is 70% by weight or more and 85% by weight or less, and the alkyl has 1 to 4 carbon atoms. The curable composition according to any one of claims 1 to 3, which is an unsubstituted alkyl group. According to any one of claims 1 to 4, the proportion of methyl methacrylate in the constituent monomer units of the (meth) acrylic acid ester-based polymer (B) is 70% by weight or more and 85% by weight or less. The curable composition according to description. The curing according to any one of claims 1 to 5, wherein the weight ratio of the polyoxyalkylene polymer (A): (meth) acrylic acid ester polymer (B) is 75:25 to 50:50. Sex composition. The curable composition according to any one of claims 1 to 6, wherein the polyoxyalkylene polymer (A) has a branched-chain polymer skeleton. A cured product obtained by curing the curable composition according to any one of claims 1 to 7.