JP2021055016A - Curable composition - Google Patents

Abstract

To provide a curable composition that has a reactive silicon group-containing polymer and a dehydrator, shows quick curability, and gives a cured product having excellent storage stability.SOLUTION: A curable composition has: a reactive silicon group-containing 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 represents 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 dehydrator (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). It is also known that a dehydrating agent is added to the reactive silicon group-containing polyoxyalkylene polymer to adjust the storage stability.

Japanese Unexamined Patent Publication No. 52-73998

The conventional curable composition containing the conventional reactive silicon group-containing polymer and the dehydrating agent does not have a sufficient curing rate, and there is room for improvement in this respect.

In view of the above situation, the present invention provides a curable composition containing a reactive silicon group-containing polymer and a dehydrating agent, which provides a cured product which exhibits fast curability and has excellent storage stability. The purpose.

The first of the present invention is 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)
The reactive silicon group-containing polymer (A) and the dehydrating agent (B) having the reactive silicon group (a) represented by, and having an unsaturated bond in the atom adjacent to the reactive silicon group (a). ) Containing a curable composition.

（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。 Preferably, the reactive silicon group-containing 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.)
It has at least one structure selected from the group consisting of the structures represented by.

（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。 Preferably, the reactive silicon group-containing polymer (A) has 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.

The reactive silicon group (a) may be a dimethoxymethylsilyl group.

The reactive silicon group (a) may be a trimethoxysilyl group and / or a (methoxymethyl) dimethoxysilyl group.

Preferably, the main chain skeleton of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer.

Preferably, the dehydrating agent (B) is a silicon compound.

Preferably, the dehydrating agent (B) is a silicon compound having a trimethoxysilyl group.

Preferably, the dehydrating agent (B) is vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, (methoxymethyl) trimethoxysilane, N- (trimethoxysilylmethyl) -O-methyl-carbamate and average. At least one or more silicon compounds selected from the group consisting of tetrameric methylsilicates.

Preferably, the content of the dehydrating agent (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A).

The curable composition preferably further contains a silanol condensation catalyst (C).

The second aspect of the present invention relates to a cured product obtained by curing the curable composition.

According to the present invention, it is possible to provide a curable composition containing a reactive silicon group-containing polymer and a dehydrating agent, which provides a cured product which exhibits fast curability and has excellent storage stability.

<< Reactive Silicon Group-Containing Polymer (A) >>
The reactive silicon group-containing 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 reactive silicon group-containing 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 reactive silicon group-containing polymer (A) is a novel reactive silicon group-containing polymer that has not been reported so far.

In the reactive silicon group-containing polymer (A), the condensation reactivity of the reactive silicon group is remarkably enhanced by the fact that the atom adjacent to the reactive silicon group has an unsaturated bond. Therefore, the reactive silicon group-containing polymer (A) that satisfies the above requirements for the reactive silicon group exhibits excellent quick-curing property even under the condition of low activity catalyst addition.

<Reactive silicon group (a)>
The reactive silicon group (a) in the reactive silicon group-containing 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 reactive silicon group-containing polymer (A) is preferably 0.5 or more, more preferably 1.0 or more on average, and 1 . 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 reactive silicon group-containing polymer (A) is more than 0.8 from the viewpoint of easily obtaining the desired effect. Is 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 reactive silicon group-containing polymer (A).

In the reactive silicon group-containing 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 reactive silicon group-containing 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 reactive silicon group-containing 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 reactive silicon group-containing 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 reactive silicon group-containing polymer (A) may be linear or may have a branched chain.
The main chain skeleton of the reactive silicon group-containing polymer (A) is not particularly limited. As the reactive silicon group-containing polymer (A), polymers having various main chain skeletons can be used. Examples of the main chain skeleton of the reactive silicon group-containing polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxy. Polyoxyalkylene polymers such as propylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and / Or Saturated carbonized polymer such as polybutadiene, isoprene or butadiene and acrylonitrile, styrene or the like, and hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin-based polymers. Hydrogen-based polymer; Polyester-based polymer; (Meta) acrylic acid ester-based polymer obtained by radical polymerization of (meth) acrylic acid ester-based monomer such as ethyl (meth) acrylate and butyl (meth) acrylate, and ( Meta) Vinyl-based polymers such as polymers obtained by radical polymerization of monomers such as acrylic acid-based monomers, vinyl acetate, acrylonitrile, and styrene; graft weights obtained by polymerizing vinyl monomers in the above-mentioned polymers. Examples thereof include organic polymers such as coalescence; polysulfide-based polymer; polyamide-based polymer; polycarbonate-based polymer; diallyl phthalate-based polymer; Each of the above polymers may be mixed in a block shape, a graft shape, or the like. Among these, saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers have a relatively low glass transition temperature, and the obtained cured product has excellent cold resistance. Therefore, a polyoxyalkylene polymer is more preferable, and polyoxypropylene is particularly preferable.

The reactive silicon group-containing 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 reactive silicon group-containing 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 reactive silicon group-containing polymer (A).

As for the molecular weight of the reactive silicon group-containing polymer (A), the polymer precursor before the introduction of the reactive silicon group is prepared according to the method for measuring the hydroxyl value of JIS K 1557 and 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 measuring method and indicate it by 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). You can. For the terminal group-equivalent molecular weight of the reactive silicon group-containing 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 is prepared, and the reactive silicon group is formed. It is also possible to convert the number average molecular weight obtained by GPC of the contained polymer into the terminal group equivalent molecular weight.

The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing 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 reactive silicon group-containing polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Method for synthesizing the reactive silicon group-containing polymer (A)>
Next, a method for synthesizing the reactive silicon group-containing polymer (A) will be described.

(Polyoxyalkylene polymer)
When the main chain of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer, a hydroxyl group-containing initiator using a composite metal cyanate complex catalyst such as zinc hexacyanocobaltate glyme complex can be used. After obtaining a hydroxyl-terminal polyoxyalkylene polymer by a method of polymerizing an epoxy compound, (i) a carbon-carbon triple bond is introduced into the hydroxyl group of the obtained hydroxyl-terminal polyoxyalkylene polymer, and then carbon- A method of adding a reactive silicon group-containing hydrosilane compound to a carbon triple bond by a hydrosilylation reaction, (ii) a reaction between the obtained hydroxyl group-terminated polyoxyalkylene polymer and a group that reacts with a hydroxyl group (for example, an isocyanate group). A method of reacting a sex silicon group and a compound having a carbon-carbon double bond, and a weight having an isocyanate group at the terminal by reacting a (iii) hydroxyl group-terminated polyoxyalkylene polymer with an excess polyisocyanate compound. After the coalescence, a method of reacting a group having an isocyanate group (for example, an amino group), a reactive silicon group, and a compound having a carbon-carbon double bond is preferable.
Among these methods, the method (i) is more preferable 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 polymer are stable.
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 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), an alkali metal salt is allowed to act on the hydroxyl group terminal-containing polymer, and then a halogenated hydrocarbon compound having a carbon-carbon triple bond is reacted. It is preferable to use the method. 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 acid ester polymer)
When the main chain of the reactive silicon group-containing polymer (A) is a (meth) acrylic acid ester-based polymer, the method for producing the reactive silicon group-containing polymer (A) is (I) polymerizable. A compound having an unsaturated group and a reactive functional group (for example, acrylate, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth) acrylic structure to obtain a polymer, and then the obtained weight is obtained. A method of introducing a carbon-carbon triple bond at any position (preferably at the end of the molecular chain) in the coalescence, and then adding a reactive silicon group-containing hydrosilane compound to the carbon-carbon triple bond by a hydrosilylation reaction, (II. ) After polymerizing a monomer having a (meth) acrylic structure by a living radical polymerization method such as atomic transfer radical polymerization to obtain a polymer, at any position (preferably at the end of the molecular chain) in the obtained polymer. Examples thereof include a method of introducing a carbon-carbon triple bond and then adding a reactive silicon group-containing hydrosilane compound to the carbon-carbon triple bond by a hydrosilylation reaction.

(Saturated hydrocarbon polymer)
When the main chain of the reactive silicon group-containing polymer (A) is a saturated hydrocarbon-based polymer, the method for producing the reactive silicon group-containing polymer (A) includes ethylene, propylene, 1-butene, and the like. After polymerizing an olefin compound having 2 to 6 carbon atoms such as isobutylene as a main monomer to obtain a polymer, a carbon-carbon triple at any position (preferably at the end of the molecular chain) of the obtained polymer. Examples thereof include a method of introducing a bond and then adding a reactive silicon group-containing hydrosilane compound to a carbon-carbon triple bond by a hydrosilylation reaction.

<< Dehydrating agent (B) >>
The dehydrating agent (B) contained in the curable composition will be described. In the present disclosure, the dehydrating agent (B) can physically adsorb compounds that can react with water preferentially over the reactive silicon group-containing polymer (A), inorganic salts that can take in water as water of crystallization, or water. Refers to a porous body. Due to the inclusion of the dehydrating agent (B), the curable composition has excellent storage stability. Further, by appropriately selecting the type and content of the dehydrating agent (B), the curing rate and storage stability (which can be rephrased as pot life) of the curable composition can be controlled. A known desiccant can be used as the dehydrating agent (B).

Examples of the compound capable of reacting with water include methyltrimethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethoxydiphenylsilane, and hexyltrimethoxysilane. , 1,6 bis (trimethoxyryl) hexane, vinylmethyldimethoxysilane, (methoxymethyl) trimethoxysilane, p-styryltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) ) -Γ-Aminopropylmethyldimethoxysilane, bis (3-trimethoxysilylpropyl) amine, and derivatives of these, methyl silicate in 1-8 mer, ethyl silicate in 1-8 mer, methyltriacetoxysilane , And silicon compounds such as vinyltris (2-methoxyethoxy) silane or partial hydrolysis condensates of these silicon compounds; trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthogeate, trialkyl orthoacetate such as tributyl orthoacetate, orthoacetate. Ester compounds such as trialkyl orthoacetate such as trimethyl, triethyl orthoacetate, tripropyl orthoacetate and tributyl orthoacetate; oxazolidine compounds such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidin Carbamate compounds such as N- (trimethoxysilylmethyl) -O-methyl-carbamate, N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate, N-methyl [3- (trimethoxysilyl) -propyl] carbamate; In addition, phosphorus pentoxide and the like can be mentioned.

Examples of the dehydrating agent that takes in water as water of crystallization include anhydrous calcium chloride, anhydrous magnesium sulfate, sodium hydrogen carbonate, and sodium sulfate (anhydrous bow glass).

Examples of the porous body capable of physically adsorbing water include zeolite (molecular sieves), silica gel, alumina and the like.

As the dehydrating agent (B), a silicon compound is preferable, and a silicon compound having a trimethoxysilyl group is more preferable, vinyl trimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, (methoxymethyl) trimethoxysilane, N- More preferably, at least one or more silicon compounds selected from the group consisting of (trimethoxysilylmethyl) -O-methyl-carbamate and average tetrameric methyl silicates, vinyl trimethoxysilane, (methoxymethyl) trimethoxysilane, And at least one silicon compound selected from the group consisting of N- (trimethoxysilylmethyl) -O-methyl-carbamate is particularly preferable, and vinyltrimethoxysilane is most preferable. The dehydrating agent (B) may be used alone or in combination of two or more.

The content of the dehydrating agent (B) in the curable composition is not particularly limited. 0.1 to 20 parts by weight is preferable, 0.5 to 10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable with respect to 100 parts by weight of the reactive silicon group-containing polymer (A). When the dehydrating agent (B) is used within the above range, it is easy to obtain a curable composition having excellent storage stability. The dehydrating agent (B) may be used alone or in combination of two or more.

<< Curable composition >>
The curable composition of the present invention contains a reactive silicon group-containing polymer (A), a dehydrating agent (B), and, if necessary, various additives.

The curable composition typically comprises a reactive silicon group-containing polymer (A), a dehydrating agent (B), and a silanol condensation catalyst (C) in combination.

Additives other than silanol condensation catalyst (C) include fillers; plasticizers; tixo-imparting agents; adhesive-imparting agents; antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers; physical property adjusting agents; Examples thereof include compounds containing an epoxy group; a photocurable substance; an oxygen curable substance; and a resin other than the reactive silicon group-containing polymer (A).

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 (C)>
In the curable composition, a silanol condensation catalyst (C) is used for the purpose of promoting the reaction of hydrolyzing and condensing the reactive silicon groups of the reactive silicon group-containing polymer and extending or cross-linking the polymer. You may.

Examples of the silanol condensation catalyst (C) 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 (C), fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

The silanol condensation catalyst (C) may be used in combination with two or more different catalysts.

The reactive silicon group (a) contained in the reactive silicon group-containing polymer (A) has high activity. Therefore, for the curable composition, the amount of silanol condensation catalyst (C) may be reduced, a type having low activity may be used as the silanol condensation catalyst (C), or aminosilane, which is an amino group-containing silane coupling agent, may be used as silanol. It can also be used as a condensation catalyst (C). Aminosilane is usually added as an adhesive-imparting agent. Therefore, when aminosilane is used as the silanol condensation catalyst (C), a curable composition that does not use the commonly used silanol condensation catalyst can be prepared. Therefore, it is preferable not to add another silanol condensation catalyst (C). 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 the silanol condensation catalyst (C).

The typical amount of the silanol condensation catalyst (C) used is 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). More preferably, 0.01 to 10 parts by weight is particularly preferable.

As for the amount of the silanol condensation catalyst (C) 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 (C), reactive silicon With respect to 100 parts by weight of the group-containing polymer (A), 0.001 to 10 parts by weight is preferable, 0.001 to 5 parts by weight is more preferable, 0.001 to 1 part by weight is further preferable, and 0.001 to 1 part by weight. 0.5 parts by weight is particularly preferable.

When aminosilane, which is an amino group-containing silane coupling agent, is used as the silanol condensation catalyst (C), the amount of the silanol condensation catalyst (C) used is 100 parts by weight of the reactive silicon group-containing polymer (A). , 0.001 to 10 parts by weight is preferable, and 0.001 to 5 parts by weight is particularly preferable.

When the blending amount of these silanol condensation catalysts (C) is within the above range, the curing can proceed at a sufficiently high speed while maintaining the curing rate so that the work can be easily performed. , The storage stability of the curable 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 (C), but is a carboxylic acid. When a metal salt, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid or the like is used as the silanol condensation catalyst (C), 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 (C). Curability tends to deteriorate when the amount of amine compound is reduced. Further, when an organic tin compound, a carboxylic acid, an alkoxy metal, an inorganic acid or the like is used as the silanol condensation catalyst (C), the curability may be deteriorated.

However, with respect to the reactive silicon group-containing polymer (A), particularly the reactive silicon group-containing polymer (A) having a structure represented by any of the general formulas (2) to (4), any of the reactivity is required. Even in combination with a silicon group and a silanol condensation catalyst (C), the activity is high and good curability is exhibited.

<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, and calcined silitin, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, Examples thereof include silicic anhydride, 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, particularly preferably 10 to 250 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

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, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<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. Further, polyoxypropylene having a reactive silicon group and the like can be mentioned.

The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). 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.

<Thixotropic agent>
A thixotropy-imparting agent can be added to the curable composition. The thixotropy-imparting agent is a compound capable of imparting thixotropy by addition. As a result, sagging can be prevented and workability can be improved.

Examples of the thixo-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Examples of the product name include Disparon 6500, Disparon 308, and Disparon 6300. The thixotropic agent may be used alone or in combination of two or more.

The amount of the thixotropy-imparting agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A).

<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, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

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

<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, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<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, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<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, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<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, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<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 of the reactive silicon group-containing polymer (A).

<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, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). 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, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). 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.

When the curable composition is a one-component type, all the compounding components are pre-blended. Therefore, the moist-containing compounding components are used after being dehydrated and dried in advance, or by reducing the pressure during compounding and kneading. It is preferably dehydrated. By adding the dehydrating agent (B) after the dehydration drying, the storage stability is further improved.

<< 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.

A curable composition containing the reactive silicon group-containing polymer (A) according to the present invention, particularly the reactive silicon group-containing polymer (A) having a structure represented by any of the general formulas (2) to (4). Can be cured in a significantly shorter time than a 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.

(Number average molecular weight)
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
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. The propylene oxide was polymerized to obtain polyoxypropylene (P-1) having a hydroxyl group at the terminal and having a number average molecular weight of 17,300 and a molecular weight distribution of Mw / Mn = 1.28.

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 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-1) 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-1) had an average of 0.7 trimethoxysilyl groups at one terminal. In the polymer (A-1), the carbon atom adjacent to the trimethoxysilyl group has a carbon-carbon double bond.

(Synthesis Example 2) 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, 1.5 molar equivalents of allyl chloride were further added to the hydroxyl group of the polymer (P-1) 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-2) having an allyl 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 7.5 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'-1) having a trimethoxysilyl group at the terminal and having a number average molecular weight of 19,400. Obtained. It was found that the polymer (A'-1) had an average of 0.7 trimethoxysilyl groups at one end.

(Examples 1 to 6, Comparative Examples 1 to 2)
According to the composition (weight ratio) shown in Table 1, first, for each polymer, Shiraishi CCR (Shiraishi Calcium Co., Ltd .: precipitated calcium carbonate) was used as a filler, and DINP (J-Plus Co., Ltd .: phthal) was used as a plasticizer. Diisononyl acid acid) was mixed and passed through a three-roll mill (manufactured by Kodaira Seisakusho Co., Ltd.) three times to uniformly disperse. A predetermined amount of various dehydrating agents (B) is added to this, and after mixing well with a spatula, stirring and defoaming are performed using a rotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: Awatori Rentaro). It was. Then, DBU (Nacalai Tesque Co., Ltd .: 1,8-diazabicyclo [5,4,0] undecene-7) was added as a condensation catalyst, mixed well with a spatula, and then stirred and removed using a rotation / revolution mixer. Foaming was performed to obtain a curable composition. The results of the skinning time of the curable composition are shown in Table 1.

(Leather time)
Under the conditions of 23 ° C. and 50% relative humidity, the obtained 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 time from the curing start time to the time when the surface was touched with a spatula and the composition did not adhere to the spatula was defined as the skinning time.

The explanation of terms in Table 1, Table 2 and Table 3 is as follows.
A-171: Momentive Performance Materials Holdings Inc. Vinyl trimethoxysilane Z-6366: Toray Dowcorning phenyltrimethoxysilane Z-6124: Toray Dowcorning methyltrimethoxysilane MMTMS: (methoxymethyl) trimethoxysilane XL-63: Wacker Chemie N- ( Trimethoxysilylmethyl) -O-methyl-carbamate Methyl silicate 51: manufactured by Corcote Co., Ltd., tetramethoxysilane condensate, average tetramer

As shown in Table 1, the curable composition of Example has a shorter skinning time than Comparative Example 1. From the comparison between each example and the comparative example, it can be seen that by using the reactive silicon group-containing polymer (A), the skinning time is shortened, and the curable composition of the example exhibits fast curing property.

(Examples 7 to 9, Comparative Example 3)
According to the composition (weight ratio) shown in Table 2, various dehydrating agents (B) and DBU as a condensation catalyst were added to (A-1) as the polymer (A), mixed well with a spatula, and then rotated. -A curable composition was obtained by stirring and defoaming using a revolution mixer. Immediately after obtaining the curable composition, the skinning time and viscosity, and the skin after transferring the obtained curable composition to a sealable glass container, sealing the container and storing at 23 ° C. for 3 days. The tension time and viscosity were measured to evaluate changes in skin tension time and viscosity before and after storage. The viscosity was measured by the measuring method shown as viscosity A. The results are shown in Table 2.

(Viscosity A)
BM type viscometer manufactured by Tokyo Keiki Co., Ltd. at 23 ° C. and 50% RH, rotor No. Viscosity at 6 rpm was measured using 4.

As shown in Table 2, it can be seen from the comparison between each example and the comparative example that the curable composition containing the reactive silicon group-containing polymer (A) and the dehydrating agent (B) is excellent in storage stability. ..

(Examples 10 to 12)
A one-component curable composition was prepared according to the composition (weight ratio) shown in Table 3 using a 5 L planetary mixer (manufactured by Dalton Co., Ltd .: 5XDMV-01-r). First, as fillers, Shiraishi CCR, Shiraishi SB (manufactured by Shiraishi Calcium Co., Ltd .: heavy calcium carbonate), and Typake R-820 (manufactured by Ishihara Sangyo Co., Ltd .: rutile-type titanium oxide) were used at 120 ° C. for 2 hours. It was dried under reduced pressure. Next, the polymer (A) was (A-1), the plasticizer was DIDP (manufactured by J-PLUS Co., Ltd .: diisodecyl phthalate), and the thixo-imparting agent was Disparon 6500 (manufactured by Kusumoto Kasei Co., Ltd .: tyxo-imparting agent). ), Tinuvin 326 (manufactured by BASF Japan, Inc .: UV absorber) as an ultraviolet absorber, and Tinuvin 770 (manufactured by BASF Japan, Inc .: light stabilizer) as a light stabilizer were put into a mixer and kneaded at 120 ° C. for 10 minutes. .. The obtained mixture was taken out and passed through a three-roll mill once to uniformly disperse the mixture, and then the mixture was put into the mixer again and dehydrated under reduced pressure at 120 ° C. for 2 hours.

After cooling the mixture to 50 ° C. or lower, various dehydrating agents (B), A-1120 (Momentive Performance Materials Holdings Inc.: γ- (2-aminoethyl) aminopropyltrimethoxysilane) as an adhesive-imparting agent, DBU was added as a condensation catalyst and kneaded for 3 minutes. After defoaming under reduced pressure for 2 minutes, the obtained mixture was immediately filled in a moisture-proof aluminum cartridge and sealed to obtain a curable composition. The skinning time and viscosity of the curable composition immediately after being obtained, and the skinning time and viscosity after storing the obtained curable composition at 50 ° C. for 4 weeks were measured, and the skinning time and before and after storage were measured. The change in viscosity was evaluated. The viscosity was measured by the measuring method shown as viscosity B. The results are shown in Table 3.

(Viscosity B)
BS type viscometer manufactured by Toki Sangyo Co., Ltd. at 23 ° C. and 50% RH, rotor No. Using No. 7, the viscosity, viscosity ratio (2 rpm / 10 rpm) and viscosity thickening rate (2 rpm, before and after storage) at 1, 2, and 10 rpm were measured.

As shown in Table 3, it can be seen that the curable composition containing the reactive silicon group-containing polymer (A) and the dehydrating agent (B) is excellent in storage stability.

Claims (12)

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)
The reactive silicon group-containing polymer (A) and the dehydrating agent (B) having the reactive silicon group (a) represented by, and having an unsaturated bond in the atom adjacent to the reactive silicon group (a). ), A curable composition. The reactive silicon group-containing 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 reactive silicon group-containing 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 curable composition according to any one of claims 1 to 5, wherein the main chain skeleton of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer. The curable composition according to any one of claims 1 to 6, wherein the dehydrating agent (B) is a silicon compound. The curable composition according to any one of claims 1 to 6, wherein the dehydrating agent (B) is a silicon compound having a trimethoxysilyl group. The dehydrating agent (B) contains vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, (methoxymethyl) trimethoxysilane, N- (trimethoxysilylmethyl) -O-methyl-carbamate and an average tetramer. The curable composition according to any one of claims 1 to 6, which is at least one or more silicon compounds selected from the group consisting of methyl silicates of the above. The item according to any one of claims 1 to 9, wherein the content of the dehydrating agent (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A). Curable composition. The curable composition according to any one of claims 1 to 10, further containing a silanol condensation catalyst (C). A cured product obtained by curing the curable composition according to any one of claims 1 to 11.