JP2021055012A - Curable composition - Google Patents

Abstract

To provide a curable composition that has a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylate copolymer, gives a cured product showing excellent strength and elongation and has improved curability.SOLUTION: A curable composition has: a polyoxyalkylene polymer (A) having a reactive silicon group (a) represented by general formula (1): -Si(R1)3-a(X)a (1) (where R1 independently represents a C1-20 hydrocarbon group, the hydrocarbon group optionally has a hetero-containing group, X independently represent a hydroxy group or hydrolyzable group, and a is 1, 2, or 3), where an atom adjacent to the reactive silicon group (a) has an unsaturated bond; and a (meth) acrylate copolymer (B) having a reactive silicon group (b).SELECTED DRAWING: None

Description

The present invention relates to a curable composition containing a reactive silicon group-containing polymer.

Reactive silicon group-containing polymers are known as moisture-reactive polymers, are contained in many industrial products such as adhesives, sealants, coating agents, paints, and adhesives, and are used in a wide range of fields. ..

As such a reactive silicon group-containing polymer, various polymers such as a polyoxyalkylene-based polymer having a main chain skeleton, a saturated hydrocarbon-based polymer, and a (meth) acrylic acid ester-based copolymer are known. However, among them, the polyoxyalkylene polymer has a wide range of application because it has a relatively low viscosity at room temperature and is easy to handle, and the cured product obtained after the reaction also exhibits good elasticity.

As a method for producing a reactive silicon group-containing polyoxyalkylene polymer, for example, an epoxy compound is ring-opened polymerized to synthesize a polyoxyalkylene polymer having a hydroxyl group at the terminal, and then the hydroxyl group is carbon-carbon double. A method of converting into a double bond and performing a hydrosilylation reaction between the carbon-carbon double bond and a silane compound is known (see, for example, Patent Document 1).

Further, in Patent Document 2, a polymer in which two or more carbon-carbon double bonds are introduced per one terminal structure is synthesized, and a hydrosilylation reaction is carried out on this polymer to carry out one terminal structure. A method for producing a polymer having two or more reactive silicon groups per unit is described.

Further, in order to improve the balance between the elongation and strength of the obtained cured product and the adhesiveness and weather resistance, the copolymer of the reactive silicon group-containing polyoxyalkylene polymer and the reactive silicon group-containing (meth) acrylic acid ester-based copolymer. Curable compositions containing both coalesced compounds are also known (see, for example, Patent Documents 2 and 3).

Japanese Unexamined Patent Publication No. 52-73998 Japanese Unexamined Patent Publication No. 6-172631 International Publication No. 2013/180203

Conventionally reported curable compositions containing a reactive silicon group-containing polyoxyalkylene-based polymer and a reactive silicon group-containing (meth) acrylic acid ester-based copolymer are cured products showing good strength and elongation. However, the curing rate was not sufficient, and there was room for improvement in this respect.

In view of the above situation, the present invention provides a cured product containing a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylic acid ester-based copolymer, and exhibiting good strength and elongation. It is an object of the present invention to provide a curable composition having improved curability.

As a result of studies to solve the above problems, the present inventors have synthesized a new polymer as a reactive silicon group-containing polyoxyalkylene-based polymer, and obtained this as a reactive silicon group-containing (meth) acrylic acid ester-based polymer. We have found that a curable composition constructed in combination with a copolymer gives a cured product exhibiting good strength and elongation and exhibits fast curability, and has arrived at the present invention.

（式中、Ｒ^４は２価の連結基を表し、前記Ｒ^４が有する２つの結合手は、それぞれ、前記連結基内の炭素原子、酸素原子、窒素原子、または硫黄原子に結合している。Ｒ^２、およびＲ^３は、それぞれ独立に、水素、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基、またはシリル基を表す。Ｒ^１、Ｘ、およびａは前記の通りである。）
で表される構造からなる群より選ばれる少なくとも１種の構造を有する。
好ましくは、前記ポリオキシアルキレン系重合体（Ａ）が、一般式（５）〜（７）：

（式中、Ｒ^１、Ｘ、およびａは前記の通りである。）
で表される構造からなる群より選ばれる少なくとも１種の構造を有する。好ましくは、前記反応性ケイ素基（ａ）が、ジメトキシメチルシリル基であってよく、また、トリメトキシシリル基、及び／又は（メトキシメチル）ジメトキシシリル基であってもよい。
好ましくは、前記反応性ケイ素基（ｂ）が、一般式（１１）：
−ＳｉＲ^１１ _３−ｃＹ_ｃ （１１）
（式中、Ｒ^１１は、それぞれ独立に、置換又は無置換の炭素原子数１〜２０の炭化水素基を表す。Ｙは、それぞれ独立に、水酸基または加水分解性基を表す。ｃは１、２、又は３である。）で表される。好ましくは、前記反応性ケイ素基（ｂ）が、メチルジメトキシシリル基、及び／又は、トリメトキシシリル基である。好ましくは、前記ポリオキシアルキレン系重合体（Ａ）と前記（メタ）アクリル酸エステル系重合体（Ｂ）の重量比が、５／９５〜９５／５である。前記硬化性組成物は、シラノール縮合触媒をさらに含有することが好ましい。
また本発明は、前記硬化性組成物を硬化させてなる硬化物にも関する。 That is, the present invention has the general formula (1):
−Si (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. X is independently a hydroxyl group or a hydroxyl group. Represents a hydrolyzable group. A is 1, 2, or 3)
A polyoxyalkylene polymer (A) having a reactive silicon group (a) represented by, and an atom adjacent to the reactive silicon group (a) having an unsaturated bond, and
The present invention relates to a curable composition containing a (meth) acrylic acid ester-based polymer (B) having a reactive silicon group (b).
Preferably, the polyoxyalkylene polymer (A) is based on the general formulas (2) to (4):

(In the formula, R ⁴ represents a divalent linking group, and the ^{two bonds of the R 4} are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively. R ² and R ³ independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. R ¹ , X, and a are as described above.)
It has at least one structure selected from the group consisting of the structures represented by.
Preferably, the polyoxyalkylene polymer (A) is based on the general formulas (5) to (7):

^{(Wherein, R 1, X,} and a are as defined above.)
It has at least one structure selected from the group consisting of the structures represented by. Preferably, the reactive silicon group (a) may be a dimethoxymethylsilyl group, or may be a trimethoxysilyl group and / or a (methoxymethyl) dimethoxysilyl group.
Preferably, the reactive silicon group (b) is based on the general formula (11):
−SiR ¹¹ _3-c Y _c (11)
(In the formula, R ¹¹ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group, respectively. C is 1, 2 or 3). Preferably, the reactive silicon group (b) is a methyldimethoxysilyl group and / or a trimethoxysilyl group. Preferably, the weight ratio of the polyoxyalkylene polymer (A) to the (meth) acrylic acid ester polymer (B) is 5/95 to 95/5. The curable composition preferably further contains a silanol condensation catalyst.
The present invention also relates to a cured product obtained by curing the curable composition.

According to the present invention, a cured product containing a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth) acrylic acid ester-based copolymer, and exhibiting good strength and elongation is provided. It is possible to provide a curable composition having improved curability. According to a preferred embodiment of the present invention, since the curable composition of the present invention contains the (meth) acrylic acid ester-based polymer (B), in addition to good strength and elongation, good adhesiveness and weather resistance. A cured product having properties can be provided.

<< Polyoxyalkylene polymer (A) >>
The polyoxyalkylene polymer (A) has a general formula (1):
−Si (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. X is independently a hydroxyl group or a hydroxyl group. Represents a hydrolyzable group. A is 1, 2, or 3)
It has a reactive silicon group (a) represented by. Further, in the polyoxyalkylene polymer (A), the atom adjacent to the reactive silicon group (a), that is, the atom bonded to the silicon atom has an unsaturated bond. In this respect, the polyoxyalkylene polymer (A) is a novel reactive silicon group-containing polymer that has not been reported so far.

In the polyoxyalkylene polymer (A), the condensation reactivity of the reactive silicon group is remarkably enhanced by the atom adjacent to the reactive silicon group having an unsaturated bond. Therefore, the polyoxyalkylene polymer (A) satisfying the above requirements for the reactive silicon group exhibits excellent quick-curing property even under the condition of adding a low-activity catalyst.

<Reactive silicon group (a)>
The reactive silicon group (a) in the polyoxyalkylene polymer (A) is represented by the general formula (1):
−Si (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. X is independently a hydroxyl group or a hydroxyl group. Represents a hydrolyzable group. A is 1, 2, or 3)
It is represented by.

R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. The ^{number of carbon atoms of the hydrocarbon group as R 1} is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.

The ^{hetero-containing group that the hydrocarbon group as R 1} may have as a substituent is a group containing a hetero atom. Here, atoms other than carbon atoms and hydrogen atoms are referred to as heteroatoms.

Preferable examples of heteroatoms include N, O, S, P, Si, and halogen atoms. Regarding the hetero-containing group, the total number of carbon atoms and the number of hetero atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

Suitable examples of hetero-containing groups are hydroxyl groups; mercapto groups; halogen atoms such as Cl, Br, I, and F; nitro groups; cyano groups; methoxy groups, ethoxy groups, n-propyloxy groups, and isopropyloxy groups. Alkoxy groups such as: methylthio groups, ethylthio groups, n-propylthio groups, and alkylthio groups such as isopropylthio groups; acyl groups such as acetyl groups, propionyl groups, and butanoyl groups; acetyloxy groups, propionyloxy groups, and butanoyl groups. Acyloxy groups such as oxy groups; substituted or unsubstituted amino groups such as amino groups, methylamino groups, ethylamino groups, dimethylamino groups, and diethylamino groups; aminocarbonyl groups, methylaminocarbonyl groups, ethylaminocarbonyl groups, dimethyl Substituted or unsubstituted aminocarbonyl groups such as aminocarbonyl groups and diethylaminocarbonyl groups; cyano groups and the like.

When R ¹ is a hydrocarbon group substituted with a hetero-containing group, ^{the total number of carbon atoms and hetero atoms in R 1} is preferably 2 to 30, more preferably 2 to 18, and further 2 to 10. 2 to 6 are preferable, and 2 to 6 are particularly preferable.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms as R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Alkyl groups such as n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n-nonadecil group, and n-icosyl group; vinyl group, 2-propenyl group, 3 -Alkenyl groups such as butenyl groups and 4-pentenyl groups; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; phenyl group, naphthalene-1-yl group , Aryl groups such as naphthalene-2-yl group, o-phenylphenyl group, m-phenylphenyl group, and p-phenylphenyl group; benzyl group, phenethyl group, naphthalene-1-ylmethyl group, and naphthalene-2-ylmethyl Examples include an aralkyl group such as a group.
These hydrocarbon groups, even groups substituted with a heteroatom-containing group described above, preferred as R ^1.

Preferable examples of R ¹ include, for example, an alkyl group such as a methyl group and an ethyl group; an alkyl group having a hetero-containing group such as a chloromethyl group and a methoxymethyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group. Aryl groups such as benzyl group; aralkyl groups such as benzyl group; and the like. The R ^1, a methyl group, methoxymethyl group, and chloromethyl group is preferably a methyl group, and more preferably a methoxymethyl group, methoxymethyl group are more preferred.

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. Among these, an alkoxy group such as a methoxy group and an ethoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable, because the hydrolyzability is mild and easy to handle.

a is 1, 2, or 3. As a, 2 or 3 is preferable.

The reactive silicon group (a) is not particularly limited as long as it is a group represented by the above formula (1). The reactive silicon group (a) represented by the formula (1) includes the following general formula (1-1):
-Si (R ⁶ ) _3-b (OR ⁷ ) _b (1-1)
(In the formula, R ⁶ is independently an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, or −R ⁸ N (R ^9). ) ₂ is an N, N-dialkylaminoalkyl group, R ⁸ is a methylene group or an ethylene group, R ⁹ is a methyl group or an ethyl group, and R ⁷ is an alkyl having 1 to 6 carbon atoms. A group, an alkenyl group having 2 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms, and b is 2 or 3).
The group represented by is preferable.

Specific examples of the alkyl group having 1 to 6 carbon atoms as R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-pentyl group, n-hexyl group and the like. Of these, a methyl group and an ethyl group are preferable.
Specific examples of the haloalkyl group having 1 to 6 carbon atoms as R ⁶ include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a 2-chloroethyl group, and 2 -Bromoethyl group and the like can be mentioned. Among these, a chloromethyl group and a bromomethyl group are preferable, and a chloromethyl group is more preferable.
Specific examples of the alkoxyalkyl group having 2 to 6 carbon atoms as R ⁶ include a methoxymethyl group, a 2-methoxyethyl group, a 1-methoxyethyl group, an ethoxymethyl group, a 2-ethoxyethyl group, and an n-propyloxy group. Examples thereof include a methyl group and a 2-n-propyloxyethyl group. Among these, a methoxymethyl group, a 2-methoxyethyl group, and an ethoxymethyl group are preferable, and a methoxymethyl group is more preferable.
Specific examples of the N, N-dialkylaminoalkyl group represented by -R ⁸ N (R ⁹ ) ₂ as R ⁶ include N, N-dimethylaminomethyl group, N, N-diethylaminomethyl group, 2 Examples thereof include -N, N-dimethylaminoethyl group and 2-N, N-diethylaminoethyl group. Among these, N, N-dimethylaminomethyl group and N, N-diethylaminomethyl group are preferable, and N, N-diethylaminomethyl group is more preferable.

Specific examples of the alkyl group having 1 to 6 carbon atoms as R ⁷ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-pentyl group, n-hexyl group and the like. Of these, a methyl group and an ethyl group are preferable.
Specific examples of the alkenyl group having 2 to 6 carbon atoms as R ⁷ include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 4-pentenyl group and the like. Of these, vinyl groups and 2-propenyl groups are preferred.
Specific examples of the acyl group having 2 to 6 carbon atoms as R ⁷ include an acetyl group, a propionyl group, a butanoyl group, and a pentanoyl group. Of these, an acetyl group is preferred.

Specific examples of the reactive silicon group (a) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a dimethoxy. Ethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, And (N, N-diethylaminomethyl) diethoxysilyl group and the like, but are not limited thereto. Among these, a cured product in which a dimethoxymethylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group have good mechanical properties can be obtained, which is preferable. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are more preferable, and a trimethoxysilyl group and a (methoxymethyl) dimethoxysilyl group are particularly preferable. From the viewpoint of stability, a dimethoxymethylsilyl group and a triethoxysilyl group are more preferable, and a dimethoxymethylsilyl group is particularly preferable.

The number of reactive silicon groups (a) contained in one molecule of the polyoxyalkylene polymer (A) is preferably 0.5 or more, more preferably 1.0 or more on average. Two or more are more preferable. The upper limit is preferably 4 or less, and more preferably 3 or less.

The average ratio of the number of reactive silicon groups (a) to the number of terminals of the polymer skeleton in one molecule of the polyoxyalkylene polymer (A) is often more than 0.8 from the viewpoint of easily obtaining the desired effect. preferable. As a result, a sufficient number of reactive silicon groups are introduced at the ends, a cured product having a sufficient crosslink density can be obtained, and the strength of the cured product can be easily improved. The average ratio can exceed 1.0, but if it exceeds 1.0, the flexibility of the cured product tends to decrease. Therefore, the average ratio is preferably more than 0.8 and 1.0 or less. The numerical value of the average ratio can be determined by the method described in the examples. In addition to the methods described in Examples, the numerical value of the average ratio can also be calculated from the results of GPC measurement and NMR measurement of the polyoxyalkylene polymer (A).

In the polyoxyalkylene polymer (A), the atom adjacent to the reactive silicon group (a) has an unsaturated bond. The atom adjacent to the reactive silicon group (a) is not particularly limited, but carbon is preferable. The unsaturated bond is not particularly limited, but a carbon-carbon double bond is preferable.

The terminal structure bonded to the end of the polymer skeleton of the polyoxyalkylene polymer (A) is preferably at least one structure represented by the following general formulas (2) to (4).

(In the formula, R ⁴ represents a divalent linking group, and the ^{two bonds of the R 4} are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively. R ² and R ³ independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. .)
R ¹ , X, and a are the same as those described above.

R ⁴ is a divalent linking group. The ^{two bonds of R 4} are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively.
Here, the fact that the ^{two bonds of R 4} are bonded to the carbon atom, oxygen atom, nitrogen atom, or sulfur atom in the linking group means that the ^{two bonds of R 4} are each bonded. It means that it exists on a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in a linking group.
Specific examples of the divalent linking _{group, - (CH 2) n -} , - O- (CH 2) n -, - S- (CH 2) n -, - NR 5 - (CH 2) n -, -O-C (= O) -NR ^5- (CH ₂ ) _n- , -NR ^5- C (= O) -NR ^5- (CH ₂ ) _n- , and the like can be mentioned. Among these, -O- (CH ₂ ) _n- , -OC (= O) -NR ^5- (CH ₂ ) _n- , and -NR ^5- C (= O) -NR ^5- (CH) ₂ ) _n -is preferable, and -O-CH _2- is more preferable because the raw material is easily available. R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group as R ⁵ include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group. Be done. As n, an integer of 0 to 10 is preferable, an integer of 0 to 5 is more preferable, an integer of 0 to 2 is further preferable, 0 or 1 is particularly preferable, and 1 is most preferable.

R ² and R ³ are independently one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a silyl group. Is. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The number of carbon atoms of the aryl group is preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms of the aralkyl group is preferably 7 to 12.
Specific examples of R ² and R ³ include hydrogen; alkyl groups such as methyl, ethyl, and cyclohexyl groups; aryl groups such as phenyl and trill groups; aralkyl groups such as benzyl group and phenethyl group. Group; Examples thereof include a silyl group such as a trimethylsilyl group. Among these, hydrogen, a methyl group, and a trimethylsilyl group are preferable, hydrogen and a methyl group are more preferable, and hydrogen is further preferable.

The terminal structure of the polyoxyalkylene polymer (A) is more preferably at least one structure represented by the following general formulas (5) to (7).

In the general formula ^{(5) ~ (7),} R 1, X, and a are the same as above described. The oxygen at the left end indicates oxygen in the repeating unit located at the end of the polymer skeleton formed by connecting a plurality of repeating units, or oxygen bonded to the repeating unit located at the end of the polymer skeleton.

The terminal structure of the polyoxyalkylene polymer (A) is more preferably at least one structure represented by the following general formulas (5-1) to (7-1).

In the above general formulas (5-1) to (7-1), R ⁶ , R ⁷ , and b are the same as those described above. The oxygen at the left end indicates oxygen in the repeating unit located at the end of the polymer skeleton formed by connecting a plurality of repeating units, or oxygen bonded to the repeating unit located at the end of the polymer skeleton.

<Main chain structure>
The main chain structure of the polyoxyalkylene polymer (A) may be linear or may have a branched chain.
Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene. − Polyoxybutylene copolymer and the like can be mentioned. Each of the above polymers may be mixed in a block shape, a graft shape, or the like. Of these, polyoxypropylene is particularly preferable.

The polyoxyalkylene polymer (A) may be a polymer having any one of the above-mentioned main chain skeletons, or a mixture of polymers having different main chain skeletons. Further, the mixture may be a mixture of polymers produced separately from each other, or a mixture produced at the same time so as to have an arbitrary mixed composition.

The number average molecular weight of the polyoxyalkylene polymer (A) is not particularly limited, but the polystyrene-equivalent molecular weight in GPC is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and 3. 000 to 30,000 is particularly preferable. When the number average molecular weight is within the above range, the amount of the reactive silicon group (a) introduced is appropriate, so that the production cost is kept within an appropriate range, the viscosity is easy to handle, and the workability is excellent. It is easy to obtain the polyoxyalkylene polymer (A).

As for the molecular weight of the polyoxyalkylene polymer (A), the polymer precursor before the introduction of the reactive silicon group is used in the method for measuring the hydroxyl value of JIS K 1557 and the measurement of the raw material as specified in JIS K 0070. It is also possible to directly measure the terminal group concentration by titration analysis based on the principle of the method and indicate the terminal group equivalent molecular weight obtained in consideration of the structure of the polymer (the degree of branching determined by the polymerization initiator used). .. For the terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A), a calibration line of the number average molecular weight obtained by general GPC measurement of the polymer precursor and the terminal group-equivalent molecular weight was prepared, and a reactive silicon group was contained. It is also possible to convert the number average molecular weight obtained by GPC of the polyoxyalkylene polymer into the terminal group equivalent molecular weight.

The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited. The molecular weight distribution is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and most preferably 1.3 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Method for synthesizing polyoxyalkylene polymer (A)>
Next, a method for synthesizing the polyoxyalkylene polymer (A) will be described.
First, a hydroxyl group-terminated polyoxyalkylene polymer was obtained by a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanate complex catalyst such as zinc hexacyanocobaltate glyme complex, and then (i) obtained. A method of introducing a carbon-carbon triple bond into the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer, and then adding a reactive silicon group-containing hydrosilane compound to the carbon-carbon triple bond by a hydrosilylation reaction, (ii). A method for reacting the obtained hydroxyl group-terminated polyoxyalkylene polymer with a compound having a group that reacts with a hydroxyl group (for example, an isocyanate group), a reactive silicon group, and a carbon-carbon double bond, and (iii). A hydroxyl group-terminated polyoxyalkylene polymer is reacted with an excess polyisocyanate compound to form a polymer having an isocyanate group at the terminal, and then a group that reacts with the isocyanate group (for example, an amino group), a reactive silicon group, and a reactive silicon group. A method of reacting a compound having a carbon-carbon double bond is preferable.
Among these methods, the method (i) is the method (i) because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the obtained reactive silicon group-containing polyoxyalkylene polymer are stable. More preferred.
By using these methods, it is difficult to hydrosilylate a polymer having an allyl group terminal which is a carbon-carbon double bond, and the rate of introduction of reactive silicon groups into the polymer terminal is 80% or more. A group-containing polyoxyalkylene polymer can be obtained.

Initiators having hydroxyl groups include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight. Examples thereof include organic compounds having one or more hydroxyl groups, such as polyoxypropylene monoalkyl ether.

Examples of the epoxy compound include ethylene oxide and alkylene oxides such as propylene oxide, methyl glycidyl ether, and glycidyl ethers such as allyl glycidyl ether. Of these, propylene oxide is preferable.

Examples of the group containing a carbon-carbon triple bond include an alkynyl group. Further, at the same time as the alkynyl group, another unsaturated group such as a vinyl group, an allyl group or a metalyl group may be introduced at the hydroxyl group terminal.

As a method for introducing a carbon-carbon triple bond into the hydroxyl group terminal of (i), a halogenated hydrocarbon having a carbon-carbon triple bond after allowing an alkali metal salt to act on the hydroxyl group terminal-containing polyoxyalkylene-based polymer. It is preferable to use a method of reacting the compounds. Examples of the alkali metal salt include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide and the like. 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.

Examples of the halogenated hydrocarbon compound having a carbon-carbon triple bond used in the method (i) include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octin, and 1 -Chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1 -Butin, 1-bromo-2-octyne, 1-bromo-2-pentin, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexine, propargyl iodide, 1 -Iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octin, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne and the like can be mentioned. Of these, propargyl chloride, propargyl bromide, and propargyl iodide are more preferred. Also, at the same time as the halogenated hydrocarbon compound having a carbon-carbon triple bond, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Halogenated hydrocarbon compounds having a carbon-carbon double bond, such as, may be used.

Examples of the hydrosilane compound used in the method (i) include halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, and dichlorophenylsilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, and the like. Dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (N, N) Alkoxysilanes such as -diethylaminomethyl) dimethoxysilane and (N, N-diethylaminomethyl) diethoxysilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; bis (dimethylketoximate) methylsilane , And ketoximatesilanes such as bis (cyclohexylketoximate) methylsilane; isopropeniroxysilanes such as triisopropenyloxysilane (deacetone type) and the like.

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, ruthenium and the like, 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 chloroplatinic acid and platinum vinylsiloxane complex are preferable.

<< (Meta) Acrylic Ester Polymer (B) >>
The curable composition of the present invention further contains a (meth) acrylic acid ester-based polymer (B) having a reactive silicon group (b).

The reactive silicon group (b) contained in the (meth) acrylic acid ester polymer (B) has the following general formula (11):
−SiR ¹¹ _3-c Y _c (11)
Can be represented by.

R ¹¹ 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, still more preferably 1 to 3 carbon atoms, or 1 or 1 carbon atom number. 2 is particularly preferable. 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. ..

Examples of R ¹¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group and n-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 ¹¹ , 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.

C in the formula (11) is 1, 2 or 3. It is preferably 2 or 3. It is more preferably 3 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 2.

Examples of the reactive silicon group (b) represented by the general formula (11) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a methyldimethoxysilyl group. , Methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, n-propyldimethoxysilyl group, n-hexyldimethoxysilyl group, phenyldimethoxysilyl group, phenyldiethoxysilyl group, methyldiisopropenoxysilyl group , Methyldiphenoxysilyl group, dimethylmethoxysilyl group and the like. A methyldimethoxysilyl group is more preferable from the viewpoint of achieving both storage stability and curability of the curable composition, and trimethoxysilyl can further enhance the curability of the composition and the recoverability of the cured product. Groups are more preferred.

Further, the reactive silicon group (a) contained in the polyoxyalkylene polymer (A) and the reactive silicon group (b) contained in the (meth) acrylic acid ester polymer (B) may be the same. It may be different.

The position where the reactive silicon group (b) is bonded in the (meth) acrylic acid ester polymer (B) is not particularly limited. The reactive silicon group (b) may be bonded to the end of the polymer skeleton, may be bonded to the inside of the polymer skeleton, or may be bonded to the end and the inside of the polymer skeleton, respectively. May be good.

Here, the reactive silicon group (b) bonded to the terminal of the polymer skeleton is the reactivity bonded to the terminal of the polymer skeleton formed by connecting a plurality of monomer units. Refers to the silicon group (b).
Further, the reactive silicon group (b) bonded to the inside of the polymer skeleton is a plurality of single amounts constituting the polymer skeleton except for the monomer unit located at the end of the polymer skeleton described above. Refers to the reactive silicon group (b) attached to any of the body units. The reactive silicon group bonded to the inside of the polymer skeleton may be expressed as a reactive silicon group bonded to the polymer as a side chain.

The average number of reactive silicon groups (b) contained in one molecule of the (meth) acrylic acid ester-based polymer (B) is not particularly limited, but is preferably 0.5 to 5.0, and when the curable composition is cured. From the viewpoint of mechanical properties, 1.0 or more is more preferable, and from the viewpoint of stability of the (meth) acrylic acid ester-based polymer (B), 3.0 or less is more preferable.

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 glycidyl acrylate and glycidyl methacrylate, and diethylaminoethyl acrylate. , Diethylaminoethyl methacrylate, and the like, and examples thereof include 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; Monoalkyl and dialkyl esters of acids and fumaric acids; 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 methacrylonitrile; amide group-containing vinyl-based monomers such as acrylamide and methacrylicamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl laurate 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.

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 requiring strength such as an adhesive, it is used. The (meth) acrylic acid ester-based polymer (B) preferably has a relatively high glass transition temperature (Tg), preferably having a Tg of 0 ° C. or higher and 200 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower. Is good. Tg can be 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", under specific reaction conditions, the growth end of the polymer grows 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 dimer 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 silicon 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 above.

The method for introducing the reactive silicon group (b) into the (meth) acrylic acid ester-based 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 silicon group together with the above-mentioned monomer. Using this method, the reactive silicon group (b) tends 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 silicon group as a chain transfer agent. Using this method, the reactive silicon group (b) can be introduced at the end 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 silicon 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 silicon group, or a method of copolymerizing glycidyl acrylate and then reacting with an aminosilane compound having a reactive silicon group. An example of how to make it.
(Vii) A method for introducing a reactive silicon group (b) 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 into the end of the polymer skeleton, and by modifying this, a reactive silicon group (b) can be introduced into the end of the polymer skeleton.

Examples of the silicon compound that can be used to introduce the reactive silicon group (b) 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 silicon 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 silicon group used in the method (v) include (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) dimethoxymethylsilane, (3-mercaptopropyl) triethoxysilane, and (3-mercaptopropyl) triethoxysilane. Examples thereof include mercaptomethyl) trimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) triethoxysilane.

Examples of the compound having a functional group that reacts with the reactive silicon group and the V group used in the method (vi) include (3-isocyanuppropyl) trimethoxysilane, (3-isocyanvopropyl) dimethoxymethylsilane, and (3-isocyanabylpropyl). ) Isoissilane compounds such as triethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) dimethoxymethylsilane, (isocyanismethyl) 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. Aminosilane compounds and the like can be mentioned.

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 is used in which a double bond is introduced 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 a reactive silicon group (b) is introduced into the double bond by hydrosilylation or the like. it can.

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 silicon group at both the end and the 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 50,000, and 1 , 200-20,000 are particularly preferred. When the number average molecular weight of the (meth) acrylic acid ester 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.

The methods 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 silicon 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 95/5 to 5/95 is preferable, and 90 / 10 to 40/60 is preferable, 80/20 to 50/50 is more preferable, and 80/20 to 55/45 is even more 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, it is preferable that the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) are 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.

<< Curable composition >>
The curable composition of the present invention contains a polyoxyalkylene polymer (A), a (meth) acrylic acid ester polymer (B), and, if necessary, various additives.
The curable composition typically comprises a polyoxyalkylene polymer (A), a (meth) acrylic acid ester polymer (B), and a silanol condensation catalyst in combination.
Additives other than the silanol condensation catalyst include fillers, adhesive imparting agents, plasticizers, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property modifiers, epoxy group-containing compounds, and photocuring agents. Examples thereof include sex substances, oxygen-curable substances, and resins other than the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B).

Further, for the purpose of adjusting the curable composition or various physical properties of the cured product, additives other than the above may be added to the curable composition, if necessary. Examples of such other additives include tackifier resins, solvents, diluents, epoxy resins, surface improvers, foaming agents, curability modifiers, flame retardants, silicates, radical bans, and metal-free. Examples thereof include activators, ozone deterioration inhibitors, phosphorus-based peroxide decomposing agents, lubricants, pigments, and antifungal agents.
Hereinafter, typical additives will be described.

<Silanol condensation catalyst>
In the curable composition, the reaction of hydrolyzing and condensing the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) is promoted, and the polymer is chained. A silanol condensation catalyst may be used for the purpose of extension or cross-linking.

Examples of the silanol condensation catalyst include organotin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.

Specific examples of the organic tin compound include dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin bis (butyl maleate), dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), and dioctyl tin bis (acetylacetate). Nate), a reaction product of dibutyl tin oxide and a silicate compound, a reaction product of a dioctyl tin oxide and a silicate compound such as dioctyl tin bis (triethoxysilicate), and a reaction product of dibutyl tin oxide and a phthalate ester. Be done.

Specific examples of the metal carboxylate salt include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate. Further, as the carboxylic acid metal salt, a salt in which the following carboxylic acid and various metals are combined can be used.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), and 1. , 5-Diazabicyclo [4,3,0] Nonen-5 (DBN) and other nitrogen-containing heterocyclic compounds; guanidines such as guanidine, phenylguanidine, and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide, and Biganides such as 1-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 alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxy. Examples thereof include aluminum compounds such as aluminum ethyl acetoacetate 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.

The reactive silicon group (a) contained in the polyoxyalkylene polymer (A) has high activity. Therefore, for the curable composition, the amount of silanol condensation catalyst may be reduced, a type having low activity may be used as the silanol condensation catalyst, or aminosilane, which is an amino group-containing silane coupling agent, may be used as the silanol condensation catalyst. You can also do it. Aminosilane is usually added as an adhesive-imparting agent. Therefore, when aminosilane is used as a silanol condensation catalyst, a curable composition that does not use a commonly used silanol condensation catalyst can be produced. Therefore, it is preferable not to add another silanol condensation catalyst. In particular, when the reactive silicon group (a) is a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, excellent curability is exhibited even if only aminosilane is used as a silanol condensation catalyst.

A typical amount of the silanol condensation catalyst used is 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). Is preferable, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable.
As for the amount of the silanol condensation catalyst used, when an organic tin compound, a carboxylic acid metal salt, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid or the like is used as the silanol condensation catalyst, the polyoxyalkylene polymer (A) is used. 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, 0.001 to 1 part by weight, based on 100 parts by weight of the total of the (meth) acrylic acid ester-based polymer (B). Is more preferable, and 0.001 to 0.5 parts by weight is particularly preferable.
When aminosilane, which is an amino group-containing silane coupling agent, is used as a silanol condensation catalyst, the amount of the silanol condensation catalyst used is the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). 0.001 to 10 parts by weight is preferable, and 0.001 to 5 parts by weight is particularly preferable, based on 100 parts by weight of the total.
When the blending amount of these silanol condensation catalysts is within the above range, curing can proceed at a sufficiently high speed while maintaining a curing rate that facilitates the work, and curability. The storage stability of the composition is good.

In general, a reactive silicon group-containing polymer having a trialkoxysilyl group as a reactive silicon group exhibits good curability when an organic tin compound is used as a silanol condensation catalyst, but a carboxylic acid metal salt, When an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid or the like is used as a silanol condensation catalyst, the curability may be deteriorated.

Further, in general, a reactive silicon group-containing polymer having a methoxymethyldimethoxysilyl group as a reactive silicon group exhibits good curability when an amine compound is used as a silanol condensation catalyst, but the amine compound has a good curability. Curability tends to deteriorate when the amount is reduced. Further, when an organic tin compound, a carboxylic acid, an alkoxy metal, an inorganic acid or the like is used as a silanol condensation catalyst, the curability may be deteriorated.

However, with respect to the polyoxyalkylene polymer (A), particularly the polyoxyalkylene polymer (A) having a structure represented by any of the general formulas (2) to (4), any reactive silicon group is used. Even in combination with silanol condensation catalyst, it has high activity and good curability.

<Filler>
Various fillers can be added to the curable composition. Fillers include heavy calcium carbonate, glazed calcium carbonate, magnesium carbonate, siliceous soil, clay, talc, kaolin, silitin, calcined silitin, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, and anhydrous. Examples thereof include silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament.

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

A balloon (hollow filler) such as an organic balloon and an inorganic balloon may be added for the purpose of reducing the weight (lower specific gravity) of the cured product formed by using the curable composition. The balloon is a spherical filler having a hollow inside. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

The amount of the balloon used is preferably 0.1 to 100 parts by weight, preferably 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). Parts by weight are particularly preferred.

<Adhesive imparting agent>
An adhesiveness-imparting agent can be added to the curable composition. 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 γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and N-β-aminoethyl-γ-. Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl) aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyl Isocyanate group-containing silanes such as triethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy. Mercapto group-containing isocyanates such as silane and γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing isocyanates such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Can be mentioned.
The adhesive-imparting agent may be used alone or in combination of two or more. In addition, reactants of various silane coupling agents can also be used as an adhesive-imparting agent.

The amount of the silane coupling agent used is preferably 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). 0.5 to 10 parts by weight is particularly preferable.

In a curable composition containing a polyoxyalkylene polymer (A), particularly a polyoxyalkylene polymer (A) having a structure represented by any of the general formulas (2) to (4), the above silane cup is used. Amino group-containing silanes (aminosilanes) in the ring agent can also be used as a silanol condensation catalyst. In this case, aminosilane is an additive that has both a silanol condensation catalyst and an adhesive-imparting agent.

<Plasticizer>
A plasticizer can be added to the curable composition. 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) -1,4-benzenedicarboxylate and other terephthalate compounds; 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalate compounds; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate , And aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyllithinolate; alkyl sulfonic acid phenyl ester; phosphoric acid ester compound; trimellitic acid ester compound. Examples include chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated thalate; process oils; epoxidized soybean oil, and epoxy plasticants such as benzyl epoxystearate.

Moreover, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and the hydroxy groups of these polyether polyols are ester groups and ether groups. Examples thereof include polyethers such as derivatives converted into the above; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.

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). Parts are more preferable, and 20 to 100 parts by weight are particularly preferable. When a plasticizer is used within the above range, it is easy to obtain a curable composition capable of forming a cured product having excellent mechanical strength while obtaining the desired effect as the plasticizer. The plasticizer may be used alone or in combination of two or more.

<Sauce preventive agent>
An anti-sagging agent may be added to the curable composition, if necessary, in order to prevent sagging and improve workability. The sagging preventive agent is not particularly limited. Examples of the sagging inhibitor include polyamide waxes; hydrogenated castor oil derivatives; 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 (antioxidants) can be used in the curable composition. The use of antioxidants can enhance the weather resistance of the cured product. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, diarylamines, and polyphenols. Specific examples of the antioxidant are described in, for example, JP-A-4-283259 and JP-A-9-194731.

The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is particularly preferable.

<Light stabilizer>
A light stabilizer can be used for the curable composition. 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. As the light stabilizer, a hindered amine type is particularly preferable.

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is particularly preferable.

<UV absorber>
An ultraviolet absorber can be used for the curable composition. The use of UV absorbers 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. As the ultraviolet absorber, a benzotriazole type is particularly preferable. Preferable specific examples of the benzotriazole-based UV absorber include the commercially available names Tinubin P, Tinubin 213, Tinubin 234, Tinubin 326, Tinubin 327, Tinubin 328, Tinubin 329, and Tinubin 571 (all manufactured by BASF). ..

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .2 to 5 parts by weight is particularly preferable.

<Physical characteristic adjuster>
If necessary, a physical characteristic adjusting agent for adjusting the tensile properties of the produced cured product may be added to the curable composition. The physical property adjusting agent is not particularly limited. Physical property modifiers include, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane, and the like. Arylalkoxysilanes; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, and tris (triethyl). Examples thereof include trialkylsilylborates such as silyl) borate; silicone varnishes; and polysiloxanes. By using the physical property adjusting agent, the hardness of the cured product of the curable composition 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. Particularly, a compound that produces trimethylsilanol is preferable. 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, which are silanes by hydrolysis. Silicon compounds that produce monools can be mentioned. Specific examples thereof include phenoxytrimethylsilane and tris ((trimethylsiloxy) methyl) propane.

The amount of the physical property adjusting agent used is preferably 0.1 to 10 parts by weight, preferably 0, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). .5 to 5 parts by weight is particularly preferable.

<Compound containing epoxy group>
In the curable composition, a compound containing an epoxy group can be used. The use of a compound containing an epoxy group can enhance the resilience of the cured product. Examples of the compound containing 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), epoxyoctyl stearate, and epoxy. Examples include butyl stearate.

The amount of the epoxy compound used is preferably 0.5 to 50 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).

<Photocurable substance>
A photocurable substance can be used in the curable composition. When a photocurable substance is used, a film of the 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 substances of this type are known, such as organic monomers, oligomers, resins, and compositions containing them. As a typical substance, a monomer having one or several acrylic or methacrylic unsaturated groups, an unsaturated acrylic compound which is an oligomer or a mixture thereof, vinyl polysilicate dermatates, an azide resin and the like can be used.

The amount of the photocurable substance used is preferably 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). More preferably 0.5 to 10 parts by weight. When a photocurable substance is used within the above range, it is easy to obtain a curable composition capable of forming a cured product having excellent weather resistance, flexibility and less cracking.

<Oxygen curable substance>
Oxygen curable substances can be used in the curable composition. Examples of the oxygen-curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen-curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product to prevent the surface from stickiness and the adhesion of dust and dirt to the surface of the cured product.

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, epoxy resins, silicon resins and the like. Modifications of the resin by drying oil; 1,2-polybutadiene, 1,4-polybutadiene, and C5- obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. Examples thereof include a liquid polymer such as a polymer of C8 diene. These may be used alone or in combination of two or more.

The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, preferably 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). .5 to 10 parts by weight is more preferable. When the amount of the oxygen-curable substance used is within the above range, it is easy to obtain a sufficient effect of improving the stainability, and the tensile properties of the cured product are not easily impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

<< 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 previously compounded, sealed and stored, and then cured by the humidity in the air after construction. Further, as a curing agent, components such as a silanol condensation catalyst, a filler, a plasticizer, and water may be separately blended, and the compounding material and the polymer composition may be mixed as a two-component type before use. it can. 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 during compounding kneading. It is preferable to be done. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, (methoxymethyl) trimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. Storage stability is further improved by adding as a dehydrating agent a silicon compound capable of reacting with water, such as N- (trimethoxysilylmethyl) -O-methyl-carbamate, and γ-glycidoxypropyltrimethoxysilane. To do.

The amount of the dehydrating agent, particularly the silicon compound that can react 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, 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable.

<< Manufacturing method of cured product >>
The curable composition of the present invention is adjusted to a desired shape by a method such as coating, casting, or filling prior to curing.
The curable composition, which has been coated, cast, or filled and shaped, is cured in a desired environment such as, for example, room temperature and normal humidity.
The polyoxyalkylene polymer (A) according to the present invention, particularly the polyoxyalkylene polymer (A) having a structure represented by any of the general formulas (2) to (4), and a (meth) acrylic acid ester. The curable composition containing the system polymer (B) can be cured in a significantly shorter time than the curable composition containing a conventionally known reactive silicon group-containing polymer.

<< Applications >>
The curable composition of the present invention can be used as an adhesive, a sealing material for sealing construction in buildings, ships, automobiles, roads, etc., a molding agent, an adhesive, a paint, a spraying agent, and the like. Further, the cured product obtained by curing the curable composition of the present invention is suitably used as a waterproof material, a coating film waterproof material, a vibration isolator, a vibration damping material, a soundproofing material, a foaming material and the like. Since the obtained cured product is excellent in flexibility and adhesiveness, the curable composition of the present invention is more preferably used as a sealant or an adhesive among the above-mentioned applications.

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

For the terminal group-equivalent molecular weight in the examples, the hydroxyl value was determined by the measuring method of JIS K 1557, and the iodine value was determined by the measuring method of JIS K 0070, and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used) was determined. It is the molecular weight obtained in consideration.

The average number of silyl groups introduced per terminal or per molecule of the polymer shown in the examples was calculated by NMR measurement.

(Synthesis Example 1) A-1
Using polyoxypropylene glycol having a number average molecular weight of about 4,500 as an initiator, propylene oxide is polymerized with a zinc hexacyanocovalent glyme complex catalyst, and the number average molecular weight is 27,900 (terminal group conversion) having hydroxyl groups at both ends. Polyoxypropylene (P-1) having a molecular weight of 17700) and a molecular weight distribution of Mw / Mn = 1.21 was obtained.
1.1 molar equivalents of sodium methoxide was added to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene (P-1) as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.2 mol equivalent of propargyl bromide was further added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into a propargyl group. Unreacted propargyl bromide was removed by vacuum devolatile. The obtained unpurified propargyl group-terminated polyoxypropylene was mixed with n-hexane and water, and then the water was removed by centrifugation. Hexane was devolatile from the obtained hexane solution under reduced pressure to give the polymer. The metal salt was removed. From the above, polyoxypropylene (Q-1) having a propargyl group at the terminal site was obtained.
To 500 g of this polymer (Q-1), 50 mg of a platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) and 7.5 g of dimethoxymethylsilane were added to carry out a hydrosilylation reaction. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) having a dimethoxymethylsilyl group at the terminal and having a number average molecular weight of 28,500. It was. It was found that the polymer (A-1) had an average of 1.0 dimethoxymethylsilyl groups at one terminal and an average of 2.0 dimethoxymethylsilyl groups in one molecule. In the polymer (A-1), the carbon atom adjacent to the dimethoxymethylsilyl group has a carbon-carbon double bond.

(Synthesis Example 2) A-2
To 500 g of the polymer (Q-1) obtained in Synthesis Example 1, 50 mg of a platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) and 8.7 g of trimethoxysilane were added to hydrosilylate. The reaction was carried out. After reacting at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-2) having a trimethoxysilyl group at the terminal and having a number average molecular weight of 28,500. It was. It was found that the polymer (A-2) had an average of 1.0 trimethoxysilyl groups at one terminal and an average of 2.0 trimethoxysilyl groups in one molecule. In the polymer (A-2), the carbon atom adjacent to the trimethoxysilyl group has a carbon-carbon double bond.

(Synthesis Example 3) A-3
A mixture of 60% and 40% by weight of polyoxypropylene glycol having a number average molecular weight of about 4,500 and polyoxypropylene triol having a number average molecular weight of about 4,500 was used as an initiator to prepare a zinc hexacyanocobaltate glyme complex catalyst. Propylene oxide was polymerized to obtain polyoxypropylene (P-2) having a number average molecular weight of 17,300 and a molecular weight distribution of Mw / Mn = 1.28 having a hydroxyl group at the terminal.
1.1 molar equivalents of sodium methoxide was added to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene (P-2) as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.2 mol equivalent of propargyl bromide was further added to the hydroxyl group of the polymer (P-2) to convert the terminal hydroxyl group into a propargyl group. Unreacted propargyl bromide was removed by vacuum devolatile. The obtained unpurified propargyl group-terminated polyoxypropylene was mixed with n-hexane and water, and then the water was removed by centrifugation. Hexane was devolatile from the obtained hexane solution under reduced pressure to give the polymer. The metal salt was removed. From the above, polyoxypropylene (Q-2) having a propargyl group at the terminal site was obtained.
To 500 g of this polymer (Q-2), 50 mg of a platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) and 8.0 g of trimethoxysilane were added to carry out a hydrosilylation reaction. After reacting at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) having a trimethoxysilyl group at the terminal and having a number average molecular weight of 19,900. It was. It was found that the polymer (A-3) had an average of 0.7 trimethoxysilyl groups at one terminal. In the polymer (A-3), the carbon atom adjacent to the trimethoxysilyl group has a carbon-carbon double bond.

(Synthesis Example 4) A'-1
To the hydroxyl group of the polymer (P-1) obtained in Synthesis Example 1, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into an allyl group, resulting in unreacted chloride. Allyl was removed by vacuum devolatilization. The obtained unpurified allyl-terminated polyoxypropylene is mixed with n-hexane and water, and then the water is removed by centrifugation, and hexane is devolatile from the obtained hexane solution under reduced pressure to remove the metal in the polymer. The salt was removed. From the above, polyoxypropylene (Q-3) having an allyl group at the terminal was obtained.
To 500 g of this polymer (Q-3), 50 mg of a platinum divinyldisiloxane complex solution (3 wt% isopropanol solution in terms of platinum) was added, and 4.8 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain polyoxypropylene (A) having a number average molecular weight of about 28,500 having a dimethoxymethylsilyl group at the terminal. '-1) was obtained. It was found that the polymer (A'-1) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.6 dimethoxymethylsilyl groups in one molecule.

(Synthesis Example 5) A'-2
To the hydroxyl group of the polymer (P-2) obtained in Synthesis Example 3, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the polymer (P-2) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. The obtained unpurified allyl group-terminated polyoxypropylene is mixed with n-hexane and water, and then the water is removed by centrifugation, and hexane is devolatile from the obtained hexane solution under reduced pressure to form a polymer. The metal salt was removed. From the above, polyoxypropylene (Q-4) having an allyl group at the terminal site was obtained.
To 500 g of this polymer (Q-4), 50 mg of a platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) and 6.5 g of dimethoxymethylsilane were added to carry out a hydrosilylation reaction. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A'-2) having a number average molecular weight of 19,400 having a dimethoxymethylsilyl group at the terminal. Obtained. It was found that the polymer (A'-2) had an average of 0.7 dimethoxymethylsilyl groups at one terminal.

(Synthesis Example 6) B-1
412 g of isobutyl alcohol was added to a four-necked flask equipped with a stirrer, heated to 105 ° C., subjected to nitrogen substitution, and then while stirring, under a nitrogen atmosphere, methyl methacrylate 670 g, butyl acrylate 60 g, stearyl methacrylate 134 g, γ A solution of 24.8 g of azobis-2-methylbutyronitrile as a polymerization initiator in a mixture consisting of 55 g of methacoxypropyldimethoxymethylsilane, 73 g of γ-mercaptopropyldimethoxymethylsilane, and 223 g of isobutyl alcohol over 5 hours. After the dropping, a solution prepared by further dissolving 2.8 g of azobis-2-methylbutyronitrile as a polymerization initiator in 45 g of isobutyl alcohol was added dropwise over 1 hour. After that, polymerization was carried out at 105 ° C. for 2 hours, and an average of 1.3 dimethoxymethylsilyl groups having a solid content concentration of 60%, a number average molecular weight of 2,100 and a weight average molecular weight of 3,700 were contained in one molecule. A (meth) acrylic acid ester copolymer having (B-1) was obtained.

(Synthesis Example 7) B-2
537 g of isobutyl alcohol was added to a four-necked flask equipped with a stirrer, heated to 90 ° C. to perform nitrogen substitution, and then while stirring, 150 g of methyl methacrylate, 704 g of butyl acrylate, 154 g of stearyl methacrylate, and γ A mixed solution prepared by dissolving 25 g of -methacoxypropyldimethoxymethylsilane and 3 g of 2,2'-azobis (2-methylbutyronitrile) in 128 g of isobutyl alcohol was added dropwise over 7 hours. After that, polymerization was carried out at 90 ° C. for 2 hours, and an average of 1.8 dimethoxymethylsilyl groups having a solid content concentration of 60%, a number average molecular weight of 17,000 and a weight average molecular weight of 48,000. A (meth) acrylic acid ester copolymer having (B-2) was obtained.

(Synthesis Example 8) B-3
320 g of isobutyl alcohol was added to a four-necked flask equipped with a stirrer, heated to 105 ° C., and subjected to nitrogen substitution. Then, while stirring, 12 g of methyl methacrylate, 292.8 g of butyl acrylate, and 2-ethylhexyl were added to the flask in a nitrogen atmosphere. 80 g of acrylate, 7.6 g of γ-methacoxypropyldimethoxymethylsilane, 7.6 g of γ-methacoxypropyltrimethoxysilane, 40 g of isobutyl alcohol, dimethyl-2,2'-azobis (2-methylpropionate) (V- 601) 2 g of the mixed solution was added dropwise over 5 hours, and then polymerization was carried out at 105 ° C. for 1 hour. A dimethoxymethylsilyl group having a number average molecular weight of 4,200 and a weight average molecular weight of 9,400 by removing the isobutyl alcohol under heating and reduced pressure from the (meth) acrylic acid ester copolymer of the obtained isobutyl alcohol solution. A (meth) acrylic acid ester copolymer (B-3) having an average of 0.35 trimethoxysilyl groups in one molecule and an average of 0.35 trimethoxysilyl groups in one molecule was obtained.

(Synthesis Example 9) B-4
The inside of the stainless steel reaction vessel with a stirrer was deoxidized, 7.7 g of cuprous bromide, 141 g of butyl acrylate, 22 g of ethyl acrylate, and 37 g of stearyl acrylate were charged and stirred by heating. 90 g of acetonitrile and 10.7 g of diethyl 2,5-dibromoadipate as an initiator are added and mixed, and pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) is added at the stage where the temperature of the mixture is adjusted to about 80 ° C. for polymerization. The reaction was initiated. 566 g of butyl acrylate, 86 g of ethyl acrylate and 149 g of stearyl acrylate were sequentially added to proceed with the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization was 1.4 g. Polymerization is carried out while adjusting the internal temperature to about 80 ° C. to about 90 ° C., and when the monomer conversion rate (polymerization reaction rate) is about 95% or more, the volatile matter is removed by devolatile under reduced pressure to remove the polymer concentrate. Got To this concentrate, 200 g of 1,7-octadien (hereinafter abbreviated as diene or octadiene) and 360 g of acetonitrile were added, and 3.1 g of triamine was added. While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react octadiene at the polymer ends. Acetonitrile and unreacted octadiene were removed by volatilization under reduced pressure to obtain a polymer concentrate having an alkenyl group at the terminal.

The above concentrate is diluted with butyl acetate, a filtration aid, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyoward 500SH: manufactured by Kyowa Chemical Industry Co., Ltd.) are added and heated to about 80 to 100 ° C. After stirring, the solid components were filtered off. The filtrate was concentrated to obtain a crude polymer product. Further, a crude polymer product, a heat stabilizer (Smilizer GS: manufactured by Sumitomo Chemical Co., Ltd.), and an adsorbent (Kyoward 700SEN, Kyoward 500SH) were added, and the temperature was raised while devolatile under reduced pressure and heated and stirred. The mixture was heated and stirred for several hours at a high temperature of about 170 ° C. to about 200 ° C. and devolatile under reduced pressure. Adsorbents (Kyoward 700SEN, Kyoward 500SH) were added, about 10 parts by weight of butyl acetate was added to the polymer, and the mixture was further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for about several hours. The treatment liquid was further diluted with butyl acetate, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

For 500 g of the polymer obtained by the above method, 9.5 g of methyldimethoxysilane (DMS), 2.5 g of methyl orthoate (MOF), and a platinum catalyst [bis (1,3-divinyl-1,1,3,3) -Tetramethyldisiloxane) platinum complex catalyst isopropanol solution] 5 mg was mixed, and the mixture was heated and stirred at about 100 ° C. After heating and stirring for about 1 hour, unreacted volatile components such as DMS were distilled off under reduced pressure to obtain a polymer (B-4) having a methyldimethoxysilyl group at both ends. The obtained polymer (B-4) had a number average molecular weight of 40,500, a molecular weight distribution of 1.3, and the number of silyl groups introduced per molecule was 2.0.

(Comparative Example 1)
The solution of the methacrylate copolymer (B-2) obtained in Synthesis Example 7 is a reactive silyl group-containing polyoxypropylene (A) so that the polymer (B-2) has a solid content of 30 parts by weight. '-1) The mixture was uniformly mixed with 70 parts by weight, and isobutyl alcohol was distilled off with a rotary evaporator to obtain a polymer mixture. With respect to 100 parts by weight of the obtained polymer mixture, 3 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) as a dehydrating agent and Neostan S-1 (manufactured by Nitto Kasei Co., Ltd .: dioctyl) as a silanol condensation catalyst. After mixing 0.5 parts by weight of tin bis (triethoxysilicate), centrifugal defoaming was performed to obtain a curable composition.

(Leather time)
Under the conditions of 23 ° C. and 50% relative humidity, the curable composition was filled in a mold having a thickness of about 5 mm using a spatula, and the time when the surface was flattened was defined as the curing start time. The surface was touched with a spatula, and the time during which the composition did not adhere to the spatula was defined as the skinning time. The results are shown in Table 1.

(Dumbbell tension physical characteristics)
The curable composition was filled in a mold and cured under the conditions of 23 ° C. and 50% relative humidity for 3 days and then at 50 ° C. for 4 days to prepare a sheet-like cured product having a thickness of about 3 mm. The obtained sheet-like cured product was punched into a No. 3 dumbbell mold and subjected to a tensile strength test under the conditions of 23 ° C. and 50% relative humidity. The strength at break (TB) and the elongation at break (EB) were measured. The test was carried out using an autograph (AGS-J) manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 1.

(Examples 1 to 3)
A curable composition was obtained by the same method as in Comparative Example 1 using the polymer (A-1), (A-2), or (A-3) instead of the polymer (A'-1). The obtained curable composition was used for the same evaluation as in Comparative Example 1. The results are shown in Table 1.

(Comparative Example 2)
The solution of the methacrylate copolymer (B-1) obtained in Synthesis Example 6 is a reactive silyl group-containing polyoxypropylene (A) so that the polymer (B-1) has a solid content of 40 parts by weight. '-2) The mixture was uniformly mixed with 60 parts by weight, and isobutyl alcohol was distilled off with a rotary evaporator to obtain a polymer mixture. After mixing 50 parts by weight of DINP as a plasticizer, 3 parts by weight of A-171 as a dehydrating agent, and 0.5 part by weight of Neostan S-1 as a silanol condensation catalyst with 100 parts by weight of the obtained polymer mixture, Centrifugal defoaming was performed to obtain a curable composition. The obtained curable composition was used for the same evaluation as in Comparative Example 1. The results are shown in Table 1.

(Example 4)
A curable composition was obtained by using the polymer (A-3) instead of the polymer (A'-2) by the same method as in Comparative Example 2. The obtained curable composition was used for the same evaluation as in Comparative Example 1. The results are shown in Table 1.

(Comparative Examples 3 to 4, Examples 5 to 7)
50 parts by weight of DINP as a plasticizer, 3 parts by weight of A-171 as a dehydrating agent, and 0.5 parts by weight of Neostan S-1 as a silanol condensation catalyst with respect to 100 parts by weight of the total polymer mixed at the ratios shown in Table 1. After mixing the parts, centrifugation was performed to obtain a curable composition. The obtained curable composition was used for the same evaluation as in Comparative Example 1. The results are shown in Table 1.

From the comparison between each Example and Comparative Example in Table 1, the reactive silicon group in which the atom adjacent to the reactive silicon group has an unsaturated bond in the reactive silicon group-containing (meth) acrylic acid ester-based polymer (B). It can be seen that by using the contained polyoxyalkylene polymer (A) in combination, the skinning time is shortened, that is, the curability is improved, and the strength and elongation of the obtained cured product are good.

(Synthesis Example 10) A'-3
1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the polymer (P-1) obtained in Synthesis Example 1. After evaporating methanol by vacuum volatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1), and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.3 molar equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 1.8 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. The obtained unpurified polyoxypropylene is mixed with n-hexane and water, and then the water is removed by centrifugation, and hexane is devolatile from the obtained hexane solution under reduced pressure to remove the metal salt in the polymer. Removed. From the above, polyoxypropylene (Q-5) having a plurality of carbon-carbon unsaturated bonds at the terminal was obtained. It was found that the polymer (Q-5) had an average of 2.0 carbon-carbon unsaturated bonds introduced at one end.
To 500 g of the obtained polymer (Q-5), 50 mg of a platinum divinyldisiloxane complex solution (3 wt% isopropanol solution in terms of platinum) was added, and 9.6 g of trimethoxysilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted trimethoxysilane is distilled off under reduced pressure to carry out polyoxypropylene having a plurality of trimethoxysilyl groups at the terminals and having a number average molecular weight of 28,500. (A'-3) was obtained. It was found that the polymer (A'-3) had an average of 1.7 trimethoxysilyl groups at one terminal and an average of 3.4 in one molecule.

(Synthesis Example 11) B-5
To a four-necked flask equipped with a stirrer, 553 g of isobutyl alcohol was added and heated to 105 ° C. to perform nitrogen substitution, and then while stirring, 702 g of methyl methacrylate, 259 g of 2-ethylhexyl acrylate and γ were used in a nitrogen atmosphere. A solution prepared by dissolving 19 g of azobis-2-methylbutyronitrile as a polymerization initiator in a mixture consisting of 108 g of-methacoxypropyltrimethoxysilane, 79 g of γ-mercaptopropyltrimethoxysilane, and 175 g of isobutyl alcohol was added dropwise over 5 hours. After that, a solution prepared by further dissolving 7.6 g of azobis-2-methylbutyronitrile as a polymerization initiator in 68 g of isobutyl alcohol was added dropwise over 1 hour. After that, polymerization is carried out after 2 hours, and an average of 0.7 trimethoxysilyl groups having a solid content concentration of 60%, a number average molecular weight of 2,200, and a weight average molecular weight of 3,100 are contained in one molecule (. A meta) acrylic acid ester copolymer (B-5) was obtained.

(Example 8)
60 parts by weight of the polymer (A-2) so that the solution of the methacrylate copolymer (B-5) obtained in Synthesis Example 11 has a solid content of 40 parts by weight. The isobutyl alcohol was distilled off with a rotary evaporator to obtain a polymer mixture. 50 parts by weight of Shiraishi CCR and 50 parts by weight of Shiraishi SB (manufactured by Shiraishi Calcium Co., Ltd .: surface-untreated heavy calcium carbonate) are mixed with 100 parts by weight of the obtained polymer mixture as a filler. It was uniformly dispersed using this roll. Then, 2 parts by weight of A-171 as a dehydrating agent, 3 parts by weight of A-1120 (manufactured by Momentive Performance Materials, Inc .: γ- (2-aminoethyl) aminopropyltrimethoxysilane) as an adhesive-imparting agent, silanol condensation. 0.3 part by weight of DBU (1,8-diazabicyclo [5,4,0] undecene-7) was added as a catalyst, and the mixture was kneaded and stirred to obtain a curable composition. The obtained curable composition was used for the same evaluation as in Comparative Example 1. The results are shown in Table 2.

(Comparative Example 5)
A curable composition was obtained by the same method as in Example 8 except that the polymer (A'-3) obtained in Synthesis Example 10 was used instead of the polymer (A-2). The same evaluation as in Example 8 was performed using the obtained curable composition. The results are shown in Table 2.

From the comparison between Example 8 and Comparative Example 5, the reactive silicon group-containing poly having an unsaturated bond in the reactive silicon group-containing (meth) acrylic acid ester-based polymer (B) in which an atom adjacent to the reactive silicon group has an unsaturated bond. It can be seen that by using the oxyalkylene polymer (A) in combination, the skinning time is shortened, that is, the curability is improved, and the strength and elongation of the obtained cured product are good.

Claims (10)

General formula (1):
−Si (R ¹ ) _3-a (X) _a (1)
(In the formula, R ¹ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. X is independently a hydroxyl group or a hydroxyl group. Represents a hydrolyzable group. A is 1, 2, or 3)
A polyoxyalkylene polymer (A) having a reactive silicon group (a) represented by, and an atom adjacent to the reactive silicon group (a) having an unsaturated bond, and
A curable composition containing a (meth) acrylic acid ester-based polymer (B) having a reactive silicon group (b). The polyoxyalkylene polymer (A) has the general formulas (2) to (4):

(In the formula, R ⁴ represents a divalent linking group, and the ^{two bonds of the R 4} are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively. R ² and R ³ independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. R ¹ , X, and a are as described above.)
The curable composition according to claim 1, which has at least one structure selected from the group consisting of the structures represented by. The polyoxyalkylene polymer (A) has the general formulas (5) to (7):

^{(Wherein, R 1, X,} and a are as defined above.)
The curable composition according to claim 1, which has at least one structure selected from the group consisting of the structures represented by. The curable composition according to any one of claims 1 to 3, wherein the reactive silicon group (a) is a dimethoxymethylsilyl group. The curable composition according to any one of claims 1 to 3, wherein the reactive silicon group (a) is a trimethoxysilyl group and / or a (methoxymethyl) dimethoxysilyl group. The reactive silicon group (b) is based on the general formula (11):
−SiR ¹¹ _3-c Y _c (11)
(In the formula, R ¹¹ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group, respectively. C is 1, The curable composition according to any one of claims 1 to 5, which is represented by 2 or 3). The curable composition according to claim 6, wherein the reactive silicon group (b) is a methyldimethoxysilyl group and / or a trimethoxysilyl group. The item according to any one of claims 1 to 7, wherein the weight ratio of the polyoxyalkylene polymer (A) to the (meth) acrylic acid ester polymer (B) is 5/95 to 95/5. The curable composition according to the description. The curable composition according to any one of claims 1 to 8, further comprising a silanol condensation catalyst. A cured product obtained by curing the curable composition according to any one of claims 1 to 9.