JP2020164607A - Reactive silyl group-containing (meth) acrylate polymer and curable composition containing the same - Google Patents

Abstract

To provide a reactive silyl group-containing (meth) acrylate polymer that is added to an organic polymer having a reactive silyl group, to give excellent weather resistance to a resultant cured product, the cured product showing high elongation, and a curable composition containing the same.SOLUTION: A (meth) acrylate polymer has a reactive silyl group having a specific structure in a main chain terminal.SELECTED DRAWING: None

Description

The present invention relates to a reactive silyl group-containing (meth) acrylic acid ester-based polymer and a curable composition containing the same.

Organic polymers such as polyoxyalkylene polymers having a reactive silyl group are used as elastic sealants and adhesives for buildings because they cure at room temperature due to moisture or the like to produce a rubber-like cured product. There is.

For the purpose of improving the weather resistance of this rubber-like cured product, an organic polymer such as a polyoxyalkylene polymer having a reactive silyl group is combined with a (meth) acrylic acid ester polymer having a reactive silyl group. Is known to cure the composition obtained by adding the above (see, for example, Patent Document 1 and the like).

Japanese Unexamined Patent Publication No. 2012-214755

However, in the conventional technique as described above, the weather resistance of the cured product obtained by mixing the organic polymer having a reactive silyl group with the (meth) acrylic acid ester-based polymer having a reactive silyl group can be obtained. Although it can be improved, there is a problem that the elongation of the cured product is reduced.

One aspect of the present invention is to add a reactive silyl group to an organic polymer having a reactive silyl group, thereby imparting excellent weather resistance to the obtained cured product and causing the cured product to exhibit high elongation (reactive silyl group-containing). It is an object of the present invention to provide a meta) acrylic acid ester-based polymer and a curable composition containing the same.

As a result of diligent studies to solve the above problems, the present inventors have identified a specific (meth) acrylic acid ester-based polymer having a reactive silyl group to be added to an organic polymer such as a polyoxyalkylene-based polymer. When a (meth) acrylic acid ester-based polymer having a reactive silyl group having a structure at the end of the main chain is used, the obtained cured product is provided with excellent weather resistance and the decrease in elongation of the cured product is suppressed. We have independently found out that we can do this, and have completed the present invention.

That is, one embodiment of the present invention includes the following configurations.

[1] A (meth) acrylic acid ester-based polymer (A) having a reactive silyl group represented by the following general formula (1) at the end of the main chain:
-W-CH _2- SiR ¹ ₂ (OR ² ) ... (1)
In the general formula (1), W is -CO-O-, -CO-N (R ³ )-, -O-CO-N (R ³ )-, -N (R ³ ) -CO-O-,- A linking group selected from N (R ³ ) -CO-N (R ³ )-, -S-CO-NH-, -NH-CO-S-, and -S-, where R ³ is a hydrogen atom. Alkyl groups having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted, alkenyl having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted. It is a group or an aryl group having 6 to 18 carbon atoms, and R ¹ is an independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is an aralkyl group of 7 to 20, and R ² is an alkyl group.

[2] The (meth) acrylic acid ester-based polymer (A) according to [1], which further has the reactive silyl group in the side chain.

[3] The (meth) acrylic acid ester-based polymer (A) according to [1] or [2] and the reactive silyl group represented by the general formula (1) at the end of the main chain (meth). A curable composition containing an organic polymer (B) having a reactive silyl group at the end of the molecular chain other than the acrylic acid ester polymer (A).

[4] The curable composition according to [3], wherein the reactive silyl group of the organic polymer (B) having a reactive silyl group at the end of the molecular chain is a methyldimethoxysilyl group.

[5] The curable composition according to [3] or [4], which contains a tin-based catalyst.

[6] A cured product obtained by curing the curable composition according to any one of [3] to [5].

As a (meth) acrylic acid ester-based polymer having a reactive silyl group to be added to an organic polymer such as a polyoxyalkylene polymer, the reactive silyl group having a specific structure according to one embodiment of the present invention is used. By using the (meth) acrylic acid ester-based polymer at the end of the main chain, it is possible to impart excellent weather resistance to the obtained cured product and obtain a cured product having high elongation.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

[1. (Meta) Acrylic ester polymer (A)]
The (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has a reactive silyl group represented by the following general formula (1) at the end of the main chain. In the present specification, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
-W-CH _2- SiR ¹ ₂ (OR ² ) ... (1)
In the general formula (1), W is -CO-O-, -CO-N (R ³ )-, -O-CO-N (R ³ )-, -N (R ³ ) -CO-O-,- A linking group selected from N (R ³ ) -CO-N (R ³ )-, -S-CO-NH-, -NH-CO-S-, and -S-, where R ³ is a hydrogen atom. Alkyl groups having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted, alkenyl having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted. It is a group or an aryl group having 6 to 18 carbon atoms, and R ¹ is an independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is an aralkyl group of 7 to 20, and R ² is an alkyl group.

In the (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention, as shown in the general formula (1), the polymer and the silicon atom of the reactive silyl group are −W−. It is bound via CH _2- . Here, since the W has the structure described above, the silicon atoms of the reactive silyl group, -CH 2 _- via an oxygen atom, a nitrogen atom, bonded to electron-withdrawing heteroatom such as sulfur atom There is. That is, the silicon atom of the reactive silyl group is bonded to the α-position of the electron-withdrawing group.

The (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has a reactive silyl group having a monofunctional monoalkoxysilyl group at the α-position of the electron-withdrawing group at the end of the main chain. Have.

Conventionally, in the art, a reactive silyl group having a trialkoxysilyl group and a dialkoxysilyl group has been used as a (meth) acrylic acid ester-based polymer having a reactive silyl group, and a monoalkoxy monoalkoxy is used. There was no idea of using a reactive silyl group with a silyl group. The present inventors conducted a study based on a new idea of using a (meth) acrylic acid ester-based polymer having a reactive silyl group having a monoalkoxysilyl group, and found that the α-position of the electron-withdrawing group was examined. By using a (meth) acrylic acid ester-based polymer (A) having a reactive silyl group having a monoalkoxysilyl group at the end of the main chain, it has excellent weather resistance and high elongation. I found that I could get things.

The reason why a cured product showing high elongation can be obtained by using the (meth) acrylic acid ester-based polymer (A) having a monofunctional reactive silyl group having a monoalkoxysilyl group is that the reactive silyl group is used. By being monofunctional, as in the case of bifunctional and trifunctional reactive silyl groups, the silicon center does not serve as a cross-linking point, so the effective network length becomes longer, the modulus of the cured product decreases, and the elongation improves. Conceivable.

[1.1. Reactive silyl group]
The (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention has the following general formula (1): at the end of the main chain.
-W-CH _2- SiR ¹ ₂ (OR ² ) ... (1)
It has a reactive silyl group represented by.

Here, W is -CO-O-, -CO-N (R ³ )-, -O-CO-N (R ³ )-, -N (R ³ ) -CO-O-, -N (R ^3). ) -CO-N (R ³ )-, -S-CO-NH-, -NH-CO-S-, and -S-, where R ³ is a hydrogen atom, halogen substituted. A cyclic, linear or branched alkyl group having 1 to 18 carbon atoms, a halogen-substituted cyclic, linear or branched alkenyl group having 1 to 18 carbon atoms, or a carbon. It is an aryl group of the number 6-18. Specific examples of R ³ include an alkyl group such as a hydrogen atom, a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group. .. Of these, a hydrogen atom and a methyl group are particularly preferable. Above all, the ease, the linking group W to introduction into the main chain terminal of the reactive silyl group, -S -, - CO-O- , and -CO-N ^{(R 3)} - and more preferably ..

Further, R ¹ is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Specific examples of R ¹ include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. Of these, methyl and ethyl groups are particularly preferred.

R ² is an alkyl group. When R ² is an alkyl group, it is preferable because it has mild hydrolysis properties and is excellent in handleability. R ² may be an alkyl group, but more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and further preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Alkyl group in the form of an alkyl group, particularly preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group or an ethyl group.

More specific examples of the reactive silyl group include a dimethylmethoxysilyl group, a diethylmethoxysilyl group, a dipropylmethoxysilyl group, a dibutylmethoxysilyl group, an ethylmethylmethoxysilyl group, a dimethylethoxysilyl group, and a diethylethoxysilyl group. Dipropylethoxysilyl group, dibutylethoxysilyl group, ethylmethylethoxysilyl group, bis (chloromethyl) methoxysilyl group, (chloromethyl) methylmethoxysilyl group, bis (methoxymethyl) methoxysilyl group, (methoxymethyl) methylmethoxy Examples thereof include a silyl group, a bis (chloromethyl) ethoxysilyl group, a (chloromethyl) methylethoxysilyl group, a bis (methoxymethyl) ethoxysilyl group, and a (methoxymethyl) methylethoxysilyl group. A dimethylmethoxysilyl group, a diethylmethoxysilyl group, a dimethylethoxysilyl group, and a diethylethoxysilyl group are more preferable, and a dimethylmethoxysilyl group and a dimethylethoxysilyl group are preferable because they are versatile, have high activity, and provide good curability. Especially preferable. Only one type of these may be used, or two or more types may be used in combination.

The (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has a reactive silyl group represented by the general formula (1) at the end of the main chain. Here, having the reactive silyl group at the end of the main chain means that the reactive silyl group is bonded to at least one of the repeating units at both ends of the repeating units constituting the main chain. This means both the case where the reactive silyl group is directly attached to the end of the main chain and the case where the reactive silyl group is indirectly attached to the end of the main chain via another molecular chain. Further, the acrylic acid ester polymer (A) has one reactive silyl group in at least one of the repeating units at both ends of the repeating units constituting the main chain. It may have a plurality of the reactive silyl groups.

It can be confirmed by NMR that the (meth) acrylic acid ester-based polymer (A) has the reactive silyl group at the end of the main chain. Further, the content of the reactive silyl group (or Si) present at the end of the main chain contained in one molecule of the (meth) acrylic acid ester polymer (A) can be measured by NMR.

Since the (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention has a reactive silyl group represented by the general formula (1) at the terminal of the main chain, it is introduced into one molecule. Since the number of the reactive silyl groups to be introduced is small and the silicon center of the reactive silyl groups to be introduced does not serve as a cross-linking point, the effective network length becomes long, so that the obtained cured product is provided with excellent weather resistance. , The cured product can be made highly elongated.

The (meth) acrylic acid ester-based polymer (A) has a reactive silyl group represented by the general formula (1) at the end of the main chain, preferably on average in one molecule of 0.05 to 5. It has 0, more preferably 0.1 to 4.0, and even more preferably 0.5 to 3.0. When the number of the reactive silyl groups contained at the end of the main chain in one molecule is 0.05 or more on average, the weather resistance of the cured product is improved, which is preferable. On the other hand, if the number is 5.0 or less, the strength of the cured product is excellent and the cured product does not become brittle, which is preferable.

In addition to having the reactive silyl group represented by the general formula (1) at the end of the main chain, the (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has a reactive silyl group represented by the general formula (1). Further, the side chain may have the reactive silyl group. Here, having the reactive silyl group in the side chain means that the reactive silyl group is bonded to a repeating unit other than one repeating unit at both ends of the repeating units constituting the main chain. This includes both the case where the reactive silyl group is directly bonded to the main chain and the case where the reactive silyl group is indirectly bonded to the main chain via another molecular chain.

It can be confirmed by NMR that the (meth) acrylic acid ester-based polymer (A) has the reactive silyl group in the side chain. Further, the content of the reactive silyl group (or Si) present in the side chain contained in one molecule of the (meth) acrylic acid ester-based polymer (A) can be measured by NMR.

When the (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has the reactive silyl group in the side chain, it is easy to introduce the reactive silyl group into the side chain. Therefore, the binding group W is more preferably -CO-O-, -CO-N (R ³ )-, and -S-.

The (meth) acrylic acid ester-based polymer (A) has a reactive silyl group represented by the general formula (1) in a side chain, preferably 0.05 to 5.0 on average in one molecule. The number is 0.1 to 3.0, more preferably 0.5 to 2.0. It is preferable that the number of the reactive silyl groups contained in the side chain in one molecule is 0.05 or more on average because the weather resistance of the cured product is improved. On the other hand, if the number is 5.0 or less, the strength of the cured product is excellent and the cured product does not become brittle, which is preferable.

The (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention has a reactive silyl group represented by the general formula (1) at the terminal of the main chain and has a side chain. By having the reactive silyl group, a monofunctional reactive silyl group that does not form a relatively large number of cross-linking points can be introduced into one molecule. Therefore, when the reactive silyl group is contained in the side chain, the cured product can be more effectively stretched.

In the (meth) acrylic acid ester-based polymer (A), the reactive silyl groups represented by the general formula (1) are added to the main chain terminal and the side chain in total, preferably 0 on average in one molecule. It has .05 to 5.0 pieces, more preferably 0.1 to 4.0 pieces, still more preferably 0.5 to 3.0 pieces. When the number of the reactive silyl groups contained at the end of the main chain in one molecule is 0.05 or more on average, the weather resistance of the cured product is improved, which is preferable. On the other hand, if the number is 5.0 or less, the strength of the cured product is excellent and the cured product does not become brittle, which is preferable.

[1.2. Main chain structure of (meth) acrylic acid ester polymer (A)]
The (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention is, for example, subjected to a polymerization step of polymerizing a (meth) acrylic acid ester-based monomer as a monomer constituting a main chain, and a polymerization step. It can be produced by a method including a silyl group introduction step of introducing the reactive silyl group into the main chain terminal of the obtained polymer. The polymerization step and the silyl group introduction step may proceed at the same time, or the silyl group introduction step may be carried out after the post-polymerization step.

The (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer (A) is not particularly limited, and various ones can be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. (Meta) acrylic acid ester in which the alcohol component constituting the ester such as tert-butyl (meth) acrylic acid is a linear, branched chain or cyclic alkyl group having 1 to 4 carbon atoms; (meth) acrylic acid n- Alcohol components constituting esters such as pentyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate are linear, branched or cyclic with 5 to 7 carbon atoms. (Meta) acrylic acid ester of alkyl group; n-octyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, nonyl (meth) acrylic acid, decyl (meth) acrylic acid, dodecyl (meth) acrylic acid, ( Examples thereof include (meth) acrylic acid ester in which the alcohol component constituting the ester such as stearyl acrylate is a linear, branched or cyclic alkyl group having 8 or more carbon atoms. These monomers may be used alone or in multiples.

As a (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer (A), (meth) acrylic acid 2 as long as it does not adversely affect the effects of the present invention. -Methoxyethyl, 3-methoxybutyl (meth) acrylic acid, 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, ethylene oxide adduct of (meth) acrylic acid, (meth) acrylic acid 2,2,2-trifluoroethyl, (meth) acrylic acid 3,3,3-trifluoropropyl, (meth) acrylic acid 3,3,4,5,4-pentafluorobutyl, (meth) acrylic acid 2 -Perfluoroethyl-2-perfluorobutylethyl, trifluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2- (meth) acrylate Trifluoromethyl-2-perfluoroethyl ethyl, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, (meth) ) Dimethylaminoethyl acrylate, chloroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate and the like may be used. Further, unesterified methacrylic acid and acrylic acid can also be used as monomers constituting the main chain of the (meth) acrylic acid ester-based polymer (A).

Further, the following vinyl-based monomers can be copolymerized together with the above-mentioned (meth) acrylic acid ester-based monomers as long as the effects of the present invention are not unfavorably affected. Examples of the vinyl-based monomer are styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride. Maleic anhydride, maleic acid, monoalkyl ester and dialkyl ester of maleic acid; monoalkyl ester and dialkyl ester of fumaric acid, fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide , Dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and other maleimide-based monomers; nitrile group-containing vinyl-based monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl acetate and propionic acid Vinyl esters such as vinyl, vinyl pivalate, vinyl benzoate, vinyl cinnate; alkens such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. Be done.

[1.3. Introduction of reactive silyl group to the end of main chain]
In the (meth) acrylic acid ester-based polymer (A), as a method for introducing a reactive silyl group represented by the general formula (1) at the end of the main chain, for example, a mercapto having the reactive silyl group is used. A method of polymerizing a (meth) acrylic acid ester-based monomer using a silane compound as a chain transfer agent can be preferably used (reactive silyl group introduction method (i)).

Examples of the mercaptosilane compound having a reactive silyl group include (dimethylmethoxysilyl) methyl mercaptan, (diethylmethoxysilyl) methyl mercaptan, (dipropylmethoxysilyl) methyl mercaptan, and (ethylmethylmethoxysilyl) methyl mercaptan, (. Dimethylethoxysilyl) methyl mercaptan, (diethylethoxysilyl) methyl mercaptan, (dipropylethoxysilyl) methyl mercaptan, (ethylmethylethoxysilyl) methyl mercaptan, [bis (chloromethyl) methoxysilyl] methyl mercaptan, (chloromethylmethylmethoxy) Cyril) methyl mercaptan, [bis (methoxymethyl) methoxysilyl] methyl mercaptan, [(methoxymethyl) methyl methoxysilyl] methyl mercaptan, [bis (chloromethyl) ethoxysilyl] methyl mercaptan, [(chloromethyl) methyl ethoxysilyl] Examples thereof include methyl mercaptan, [bis (methoxymethyl) ethoxysilyl] methyl mercaptan, and [(methoxymethyl) methyl ethoxysilyl] methyl mercaptan. Only one type of these may be used, or two or more types may be used in combination.

Alternatively, a method of modifying the main chain terminal functional group of the (meth) acrylic acid ester-based polymer synthesized by the living radical polymerization method to introduce the reactive silyl group can also be used. The (meth) acrylic acid ester-based polymer obtained by the living radical polymerization method tends to introduce a functional group at the end of the main chain of the polymer, and by modifying this, the reactive silyl group is introduced at the end of the main chain. (Reactive silyl group introduction method (ii)).

In this method, any modification reaction can be used. For example, a method using a compound having a functional group capable of reacting with a terminal reactive group obtained by polymerization and a silyl group, a functional group capable of reacting with a terminal reactive group. A method of introducing a double bond at the end of the main chain of a polymer using a group and a compound having a double bond to carry out hydrosilylation, and after copolymerizing allyl (meth) acrylate, the alkene and the general A method of introducing a reactive silyl group by a method of reacting a mercaptosilane having a reactive silyl group-containing group represented by the formula (1) or the like can be used. Examples of the compound having a functional group and a silyl group capable of reacting with the terminal reactive group obtained by the above polymerization include isocyanate methyl (dimethylmethoxy) silane, isocyanatemethyl (diethylmethoxy) silane, and isocyanatemethyl (dipropylmethoxy). Silane, isocyanate methyl (ethylmethylmethoxy) silane, isocyanatemethyl (dimethylethoxy) silane, isocyanatemethyl (diethylethoxy) silane, isocyanatemethyl (dipropylethoxy) silane, isocyanatemethyl (ethylmethylethoxy) silane, isocyanatemethyl [bis (bis) Chloromethyl) methoxy] silane, isocyanate methyl [(chloromethyl) methylmethoxy] silane, isocyanate methyl [bis (methoxymethyl) methoxy] silane, isocyanate methyl (methoxymethylmethylmethoxy) silane, isocyanate methyl [bis (chloromethyl) ethoxy] ] Silane, isocyanate methyl [(chloromethyl) methyl ethoxy] silane, isocyanate methyl [bis (methoxymethyl) ethoxy] silane, isocyanate silane such as isocyanate methyl [(methoxymethyl) methyl ethoxy] silane, and the like can be used. The hydrosilanes used for hydrosilylation include bis (chloromethyl) methoxysilane, (chloromethyl) methylmethoxysilane, bis (chloromethyl) ethoxysilane, (chloromethyl) methyl ethoxysilane, and bis (methoxymethyl) methoxy. Silane, (methoxymethyl) methyl methoxysilane, bis (methoxymethyl) ethoxysilane, (methoxymethyl) methyl ethoxysilane, bis (ethoxymethyl) methoxysilane, (ethoxymethyl) methyl methoxysilane, bis (aminomethyl) methoxysilane, (Aminomethyl) methyl methoxysilane, bis (dimethylaminomethyl) methoxysilane, (dimethylaminomethyl) methyl methoxysilane, bis (diethylaminomethyl) methoxysilane, (diethylaminomethyl) methyl methoxysilane, bis [N- (2-amino) Ethyl) aminomethyl] methoxysilane, [N- (2-aminoethyl) aminomethyl] methyl methoxysilane, bis (acetoxymethyl) methoxysilane, (acetoxymethyl) methyl methoxysilane, bis (acetoxymethyl) ethoxysilane, (acetoxy) Examples thereof include hydrosilanes such as methyl) methyl ethoxysilanes. Examples of the mercaptosilane having a reactive silyl group-containing group represented by the general formula (1) to react with the alkene include (dimethylmethoxysilyl) methyl mercaptan, (diethylmethoxysilyl) methyl mercaptan, and (dipropylmethoxy). Cyril) methyl mercaptan, (ethyl methyl methoxysilyl) methyl mercaptan, (dimethyl ethoxysilyl) methyl mercaptan, (diethyl ethoxysilyl) methyl mercaptan, (dipropyl ethoxysilyl) methyl mercaptan, (ethyl methyl ethoxysilyl) methyl mercaptan, [bis (Chloromethyl) methoxysilyl] methyl mercaptan, [(chloromethyl) methyl methoxysilyl] methyl mercaptan, [bis (methoxymethyl) methoxysilyl] methyl mercaptan, [(methoxymethyl) methyl methoxysilyl] methyl mercaptan, [bis (chloro) Methyl) ethoxysilyl] methyl mercaptan, [(chloromethyl) methyl ethoxysilyl] methyl mercaptan, [bis (methoxymethyl) ethoxysilyl] methyl mercaptan, and [(methoxymethyl methyl) ethoxysilyl] methyl mercaptan and other mercaptosilane compounds Can be used. If the reactive silyl group introduction method (ii) is used, the molecular weight can be arbitrarily controlled to obtain a reactive silyl group-containing (meth) acrylic acid ester-based polymer (A) having a narrow molecular weight distribution.

[1.4. Method for Producing (Meta) Acrylic Ester Polymer (A)]
The synthetic method for polymerizing the (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer (A) is not particularly limited, and a known method can be mentioned. , Free radical polymerization method can be used. Examples of the free radical polymerization method include a solution polymerization method in which a polymerization initiator, a chain transfer agent, a solvent and the like are added and polymerization is carried out at 50 to 150 ° C., and an acrylic acid alkyl ester-based monomer described in JP-A-2001-207157. Examples include a continuous massive polymerization method in which the radical is synthesized at high temperature and high pressure.

Examples of the polymerization initiator include 2,2'-azobis (2-methylbutylonitrile), dimethyl 2,2'-azobis (2-methylpropionate), and 2,2'-azobis (2,4). -Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 1, Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, isobutylyl peroxide, isononanoyl peroxide, decanoyyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di ( Diacyl peroxides such as 3,5,5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3- Peroxydicarbonates such as methoxybutyl purge carbonate and dicyclohexyl purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethyl hexanoate, tert-butyl perisobutyrate, tert-butyl purpi. Peroxyesters such as valate, tert-butyldiper adipate, cumylper neodecanoate; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert -Dialkyl peroxides such as butylcumyl peroxide, 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as cumenhydroxyperoxide, tert-butylhydroperoxide. Examples include peroxides such as 1,1-di (tert-hexyl peroxy) -3,3,5-trimethylcyclohexane. These polymerization initiators may be used alone or in combination of two or more.

As the chain transfer agent, when the reactive silyl group is introduced by the reactive silyl group introduction method (i), a mercaptosilane compound having the reactive silyl group is used. Examples of such a mercaptosilane compound include the above 1.3. The ones described in can be used. Further, when the reactive silyl group is not introduced in the reactive silyl group introduction method (i), or in addition to the mercaptosilane compound, for example, mercapto such as n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, etc. Group-containing compounds can be used.

Examples of the solvent include aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate and di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane and the like. Hydrocarbon compounds; carboxylic acid ester compounds such as butyl acetate, n-propulate acetate, isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dialkyl carbonate compounds such as dimethyl carbonate and diethyl carbonate; 1-propanol and 2-propanol. , 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol and other alcohol compounds can be mentioned. Among these, one or more selected from a dialkyl carbonate compound and an alcohol compound are preferable from the viewpoints of not being a substance for which the guideline value of the Ministry of Health, Labor and Welfare has been established, odor, and environmental load. Further, the boiling point is measured according to the measurement method described in the February 14, 2001 edition of GEV Specification and Classification Criteria defined by GEV (Gemine Shaft Emission Control Ligewerkstoffe Ave). Dimethyl carbonate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol are more suitable because they can suppress the emission of all volatile organic compounds from the composition. Preferably, 2-propanol and isobutyl alcohol are particularly preferable.

In addition to having the reactive silyl group represented by the general formula (1) at the end of the main chain, the (meth) acrylic acid ester-based polymer (A) according to the embodiment of the present invention has a reactive silyl group represented by the general formula (1). Further, the side chain may have the reactive silyl group. The (meth) acrylic acid ester-based polymer (A) having the reactive silyl group also in the side chain is, for example, the (meth) acrylic acid ester-based monomer and the reactive silyl as a monomer constituting the main chain. It can be produced by copolymerizing with a (meth) acrylic acid ester-based monomer containing a group (reactive silyl group introduction method (iii)).

The polymer thus obtained contains a repeating unit derived from the (meth) acrylic acid ester that does not contain a reactive silyl group and a repeating unit derived from the (meth) acrylic acid ester that contains a reactive silyl group. Including. Then, the reactive silyl group is introduced into the side chain of the (meth) acrylic acid ester-based polymer (A) in the repeating unit derived from the (meth) acrylic acid ester containing the reactive silyl group. ..

The (meth) acrylic acid ester-based monomer containing the reactive silyl group is not particularly limited, and any (meth) acrylic acid ester having a reactive silyl group represented by the general formula (1) can be used. Can be used. For example, (meth) acrylic acid (dimethylmethoxysilyl) methyl, (meth) acrylic acid (diethylmethoxysilyl) methyl, (meth) acrylic acid (dipropylmethoxysilyl) methyl, (meth) acrylic acid (ethylmethyl) Methoxysilyl) methyl, (meth) acrylic acid (dimethylethoxysilyl) methyl, (meth) acrylic acid (diethylethoxysilyl) methyl, (meth) acrylic acid (dipropylethoxysilyl) methyl, (meth) acrylic acid (ethylmethyl) Ethoxysilyl) methyl, (meth) acrylic acid (dimethylpropoxysilyl) methyl, (meth) acrylic acid (diethylpropoxysilyl) methyl, (meth) acrylic acid (dipropylpropoxysilyl) methyl, (meth) acrylic acid [bis (meth) Chloromethyl) methoxysilyl] methyl, (meth) acrylic acid [(chloromethyl) methylmethoxysilyl] methyl, (meth) acrylic acid [bis (methoxymethyl) methoxysilyl] methyl, (meth) acrylic acid [(methoxymethyl)) Methylmethoxysilyl] methyl, (meth) acrylic acid [bis (chloromethyl) ethoxysilyl] methyl, (meth) acrylic acid [(chloromethyl) methylethoxysilyl] methyl, (meth) acrylic acid [bis (methoxymethyl) ethoxy Cyril] methyl, (meth) acrylic acid [(methoxymethyl) methyl ethoxysilyl] methyl, etc., include (meth) acrylic acid (dimethylmethoxysilyl) methyl, (meth) acrylic acid (diethylmethoxysilyl) methyl, ( More preferably, methyl (meth) acrylic acid (dimethylethoxysilyl) and methyl (meth) acrylic acid (diethylethoxysilyl). These monomers may be used alone or in multiples.

The (meth) acrylic acid ester-based polymer (A) is a repeating unit derived from the (meth) acrylic acid ester-based monomer containing no reactive silyl group, 80.0 to 100 parts by weight (more preferably 80.0). ~ 99.5 parts by weight, more preferably 88.0 to 99.2 parts by weight, even more preferably 92.0 to 99.0 parts by weight) and the (meth) acrylic acid ester containing the reactive silyl group. Repeating unit derived from the system monomer 0 to 20.0 parts by weight (more preferably 0.05 to 20.0 parts by weight, still more preferably 0.08 to 12.0 parts by weight, still more preferably 1.0 to 8 parts by weight. It is more preferable that the polymer contains (0.0 parts by weight). As a result, it is possible to impart excellent weather resistance to the obtained cured product and to realize high elongation of the cured product.

In other words, the (meth) acrylic acid ester-based monomer containing the reactive silyl group is more preferably 0.5% by weight based on 100% by weight of all the monomers constituting the (meth) acrylic acid ester-based polymer (A). % Or more, more preferably 0.8% by weight or more, particularly preferably 1.0% by weight or more, preferably less than 20.0% by weight, more preferably 12.0% by weight or less, particularly preferably 8.0. It is less than% by weight.

The total amount of the (meth) acrylic acid alkyl ester-based monomer is more preferably 1 to 1000 times by mole, still more preferably 8 to 500 times by mole, based on the total amount of the (meth) acrylic acid ester containing a reactive silyl group. Even more preferably, it is 10 to 200 times the molar amount.

The (meth) acrylic acid ester-based polymer (A) having the reactive silyl group also in the side chain, or, for example, after copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group, said It can also be produced by a method of reacting a compound having a reactive silyl group and a functional group that reacts with the reactive functional group (reactive silyl group introduction method (iv)). Specifically, a method of reacting this hydroxyl group with an isocyanate silane having a reactive silyl group-containing group represented by the general formula (1) after copolymerizing 2-hydroxyethyl acrylate, glycidyl (meth) acrylate. After copolymerizing, the method of reacting this epoxy group with an aminosilane compound having a reactive silyl group-containing group represented by the general formula (1), and after copolymerizing allyl (meth) acrylate, alkene. And a method of reacting a mercaptosilane having a reactive silyl group represented by the general formula (1) can be exemplified.

Examples of the compound having the reactive silyl group and the functional group that reacts with the reactive functional group used in the method include isocyanate methyl (dimethylmethoxy) silane, isocyanatemethyl (diethylmethoxy) silane, and isocyanatemethyl (dipropylmethoxy). Silane, isocyanate methyl (ethylmethylmethoxy) silane, isocyanatemethyl (dimethylethoxy) silane, isocyanatemethyl (diethylethoxy) silane, isocyanatemethyl (dipropylethoxy) silane, isocyanatemethyl (ethylmethylethoxy) silane, isocyanatemethyl [bis (bis) Chloromethyl) methoxy] silane, isocyanate methyl (chloromethylmethylmethoxy) silane, isocyanate methyl [bis (methoxymethyl) methoxy] silane, isocyanate methyl (methoxymethylmethylmethoxy) silane, isocyanate methyl [bis (chloromethyl) ethoxy] silane , Isocyanate silane compounds such as isocyanate methyl (chloromethylmethylethoxy) silane, isocyanatemethyl [bis (methoxymethyl) ethoxy] silane, and isocyanatemethyl (methoxymethylmethylethoxy) silane; aminomethyl (dimethylmethoxy) silane, aminomethyl ( Diethylmethoxy) silane, aminomethyl (dipropylmethoxy) silane, aminomethyl (ethylmethylmethoxy) silane, aminomethyl (dimethylethoxy) silane, aminomethyl (diethylethoxy) silane, aminomethyl (dipropylethoxy) silane, aminomethyl (Ethylmethylethoxy) isocyanate, aminomethyl [bis (chloromethyl) methoxy] isocyanate, aminomethyl [(chloromethyl) methylmethoxy] isocyanate, aminomethyl [bis (methoxymethyl) methoxy] isocyanate, aminomethyl [(methoxymethyl)) Methylmethoxy] silane, aminomethyl [bis (chloromethyl) ethoxy] silane, aminomethyl [(chloromethyl) methylethoxy] silane, aminomethyl [bis (methoxymethyl) ethoxy] silane, and aminomethyl [(methoxymethyl) methyl) Aminosilane compounds such as ethoxy] silane; (dimethylmethoxysilyl) methyl mercaptan, (diethylmethoxysilyl) methyl mercaptan, (dipropylmethoxysilyl) methyl mercaptan, (ethyl methyl methoxysilyl) methyl mercaptan, (dimethi) Luethoxysilyl) methyl mercaptan, (diethylethoxysilyl) methyl mercaptan, (dipropylethoxysilyl) methyl mercaptan, (ethylmethylethoxysilyl) methyl mercaptan, [bis (chloromethyl) methoxysilyl] methyl mercaptan, [(chloromethyl) Methyl methoxysilyl] methyl mercaptan, [bis (methoxymethyl) methoxysilyl] methyl mercaptan, [(methoxymethyl) methyl methoxysilyl] methyl mercaptan, [bis (chloromethyl) ethoxysilyl] methyl mercaptan, [(chloromethyl) methyl ethoxy Examples thereof include mercaptosilane compounds such as [silyl] methyl mercaptan, [bis (methoxymethyl) ethoxysilyl] methyl mercaptan, and [(methoxymethyl) methyl ethoxysilyl] methyl mercaptan.

The methods (i) to (iv) may be used in any combination. For example, by combining method (i) and method (iii), the reactive silyl group can be introduced into both the main chain terminal and the side chain.

[1.4. (Molecular weight of (meth) acrylic acid ester polymer (A)]
The weight average molecular weight of the (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention is preferably 1,000 to 100,000 in terms of polystyrene in GPC, and more preferably 1,500 to 1. It is 70,000, more preferably 2,000 to 50,000. When the weight average molecular weight of the (meth) acrylic acid ester-based polymer (A) exceeds 100,000, the compatibility with the organic polymer (B) is lowered, or the workability is lowered due to the high viscosity. It may happen. The number average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 500 to 50,000, more preferably 800 to 35,000, and even more preferably 1,000 to 25,000. Is.

The molecular weight distribution (Mw / Mn) of the (meth) acrylic acid ester-based polymer (A) according to one embodiment of the present invention is not particularly limited, but is preferably less than 4.0, more preferably 3.8 or less, and 3 5.5 or less is more preferable. The lower limit is not particularly limited, but is preferably 1 or more, and may be 1.9 or more.

The number of the reactive silyl group or Si atom in one molecule of the (meth) acrylic acid ester polymer (A) according to the embodiment of the present invention is the polystyrene-equivalent number average molecular weight by GPC and the reactive silyl group. Is calculated as the product of the concentrations (mol / g) of.

[2. Organic polymer having a reactive silyl group at the end of the molecular chain (B)]
In one embodiment of the present invention, there is also a curable composition containing the (meth) acrylic acid ester-based polymer (A) and the organic polymer (B) having a reactive silyl group at the end of the molecular chain. included. Hereinafter, the organic polymer (B) used in one embodiment of the present invention will be described. Here, in one embodiment of the present invention, the organic polymer (B) having a reactive silyl group at the end of the molecular chain is, for example, a (meth) acrylic acid ester system having a reactive silyl group at the end of the molecular chain. Although a polymer is also included, in the present invention, the organic polymer (B) having a reactive silyl group at the end of the molecular chain has a reactive silyl group represented by the general formula (1) at the end of the main chain. It means an organic polymer (B) having a reactive silyl group at the end of the molecular chain other than the (meth) acrylic acid ester-based polymer (A).

[2.1. Reactive silyl group]
The reactive silyl group of the organic polymer (B) has a general formula (2):
−SiR ⁴ _3-a X _a ... (2)
^{(R 4} are each independently a substituted or unsubstituted alkyl group from 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, aralkyl group having a carbon number of 7 to 20 or,, -OSiR _'3 ( R'is a triorganosyloxy group, each independently represented by a hydrocarbon group having 1 to 20 carbon atoms), and X is an independently hydroxy or hydrolyzable group, respectively. a is an integer from 1 to 3, more preferably 2 or 3).

Here, the organic polymer (B) having a reactive silyl group at the end of the molecular chain has a (meth) acrylic acid ester-based weight having a reactive silyl group represented by the general formula (1) at the end of the main chain. Since the organic polymer (B) having a reactive silyl group at the end of the molecular chain other than the coalescence (A) may be used, the organic polymer (B) is a polymer other than the (meth) acrylic acid ester-based polymer. In the case of, the reactive silyl group of the organic polymer (B) is not particularly limited as long as it is a reactive silyl group represented by the general formula (2).

The hydrolyzable group is not particularly limited, and specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, and an acid amide. Examples include groups, aminooxy groups, mercapto groups and the like. Of these, halogens, alkoxy groups, alkenyloxy groups, and acyloxy groups are more preferable because of their high activity. Further, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle. Further, the ethoxy group and the isopropenoxy group are preferable from the viewpoint of safety because the compounds eliminated by the reaction are ethanol and acetone, respectively.

The hydrolyzable group and the hydroxy group can be bonded to one silicon atom in the range of 1 to 3, more preferably 2 to 3. When two or more hydrolyzable groups and hydroxy groups are bonded to the reactive silyl group, the hydrolyzable groups and hydroxy groups may be the same or different.

The a in the general formula (2) is preferably 3 when quick-curing property is required, and 2 when stability during storage is required.

As specific examples of R ⁴ in the general formula (2), for example an alkyl group such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl, aralkyl groups such as benzyl group, and , Trimethylsiloxy group, chloromethyl group, methoxymethyl group and the like. Of these, the methyl group is particularly preferred.

More specific examples of the reactive silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, and a tris (2). -Propenyloxy) silyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (ethoxymethyl) dimethoxysilyl group can be mentioned. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a dimethoxymethylsilyl group is particularly preferable, because they are versatile, have high activity, and can obtain good curability. Further, from the viewpoint of storage stability, a dimethoxymethylsilyl group and a triethoxysilyl group are particularly preferable. Chloromethyldimethoxysilyl group and methoxymethyldimethoxysilyl group are preferable because they exhibit particularly high curability. A cured product obtained from an organic polymer having a trifunctional silyl group such as a trimethoxysilyl group or a triethoxysilyl group tends to have high restorability and is preferable.

[2.2. Introduction of reactive silyl group]
The reactive silyl group may be introduced by a known method. That is, for example, the following method can be mentioned.

(I) Hydrosilylation: First, an unsaturated bond is introduced into a polymer that is a raw material of the organic polymer (B) (hereinafter, may be referred to as a "precursor polymer" in the present specification), and this unsaturated bond is introduced. This is a method of adding a hydrosilane compound to a hydrosilylation reaction. Any method can be used as the method for introducing the unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is reacted with a group exhibiting reactivity with this functional group and a compound having an unsaturated group. , There are a method of obtaining an unsaturated group-containing polymer and a method of copolymerizing a polymerizable monomer having an unsaturated bond.

(II) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: A precursor polymer having a reactive group such as a hydroxyl group, an amino group or an unsaturated bond reacts with the reactive group. This is a method of reacting with a compound having both a group capable of forming a bond and a reactive silyl group (also called a silane coupling agent). The combination of the reactive group of the precursor polymer and the reactive group of the silane coupling agent includes a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, and an amino group and an epoxy group. Examples include, but are not limited to, Michael addition of an amino group and an acrylic structure, a carboxylic acid group and an epoxy group, an unsaturated bond and a mercapto group.

The method (I) is preferable because the reaction is simple, the amount of the reactive silyl group introduced can be easily adjusted, and the physical properties of the obtained reactive silyl group-containing polymer are stable. The method (II) has many reaction options, and it is easy to increase the rate of introduction of reactive silyl groups, which is preferable.

Specific examples of the hydrosilane compound used in the method (I) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. , Methyldimethoxysilane, phenyldimethoxysilane, (chloromethyl) dimethoxysilane, (methoxymethyl) dimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, Tris Alkoxysilanes such as (2-propenyloxy) silanes; acyloxysilanes such as methyldiacetoxysilanes and phenyldiacetoxysilanes; bis (dimethylketoximate) methylsilanes, bis (cyclohexylketoximate) methylsilanes Examples thereof include, but are not limited to, ketoximate silanes. Of these, halogenated silanes and alkoxysilanes are preferable in terms of availability. Alkoxysilanes are preferable because they are mildly hydrolyzable and easy to handle.

Examples of the silane coupling agent that can be used in the method (II) include the following compounds. For example, mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane that react with unsaturated bonds; 3-isocyanatepropylmethyldimethoxysilane and 3-isocyanatepropyltrimethoxy that react with hydroxyl groups. Isocyanate silanes such as silane; epoxy silanes such as 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropyltrimethoxysilane that react with hydroxyl groups, amino groups and carboxylic acid groups; isocyanate groups and thioisocyanate groups Aminosilanes such as 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyltrimethoxysilane; hydroxyalkylsilanes and the like that react with. The above-mentioned silane coupling agent is an example, and a silyl group can be introduced by utilizing or applying a similar reaction.

The number of reactive silyl groups contained in the organic polymer (B) is at least 0.5 or more, preferably 1 to 5, more preferably 1.3 to 4 in one molecule of the polymer, and further. The number is preferably 1.4 to 3.5, more preferably 1.5 to 3, and particularly from the viewpoint of high elongation and high strength, 2 to 5 is preferable, and 2 to 4 is preferable. More preferably, 2 to 3.5 pieces are further preferable. When the number of reactive silyl groups contained in the molecule is less than 0.5 on average, the curability becomes insufficient and it tends to be difficult to exhibit good rubber elastic behavior. When the number of reactive silyl groups contained in the molecule exceeds 5 on average, the cured product tends to become hard and the stretchable physical properties tend to decrease.

The organic polymer (B) has a reactive silyl group at the end of the molecular chain. That is, the reactive silyl group may be at the end of the main chain of the organic polymer (B), at the end of the side chain, or both. Here, the fact that the reactive silyl group is present at the end of the main chain means that at least one of the repeating units constituting the main chain of the organic polymer (B) is reacted with at least one of the repeating units at both ends. It is intended that the sex silyl group is directly or indirectly attached. Further, the fact that there is a reactive silyl group at the end of the side chain means that among the repeating units constituting the main chain, the reactive silyl group is attached to the side chain bonded to a repeating unit other than one repeating unit at both ends. Is intended to be directly or indirectly combined. The organic polymer (B) is an organic polymer (B) having one or more reactive silyl groups only at at least one of the ends of the main chain of the organic polymer (B), or one or more reactions. An organic polymer (B) having a sex silyl group only in a side chain bonded to at least one of the terminals of the main chain of the organic polymer (B) and its vicinity to a repeating unit can also be preferably used. In particular, when the reactive silyl group is present only at the end of the main chain of the organic polymer (B) or only at the end of the main chain and the side chains in the vicinity thereof, the organic contained in the finally formed cured product. Since the effective network length of the polymer component is long, it is easy to obtain a rubber-like cured product showing high strength and high elongation, which is preferable.

[2.3. Organic polymer (B)]
The number average molecular weight of the organic polymer (B) is about 800 to 50,000, more preferably 1,000 to 40,000, and particularly preferably 1,500 to 30,000 in terms of polystyrene in GPC. More preferably, it is 2,000 to 30,000. If the number average molecular weight of the organic polymer (B) is small, the amount of the reactive silyl group introduced is large, which may be inconvenient in terms of production cost. On the other hand, if the number average molecular weight is large, the viscosity becomes high, which tends to be inconvenient in terms of workability.

The molecular weight distribution (Mw / Mn) of the organic polymer (B) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less. 4 or less is particularly preferable. The lower limit is not particularly limited, but is preferably 1 or more, and may be 1.05 or more.

The main chain skeleton of the organic polymer (B) is not particularly limited, and those having various main chain skeletons can be used.

Specifically, polyoxyalkylene-based weights such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Combined; ethylene-propylene-based copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and apolymer of acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymers of acrylonitrile and styrene, etc., hydrocarbon-based polymers such as hydrogenated polyolefin-based polymers obtained by hydrogenating these polyolefin-based polymers; condensation of dibasic acids such as adipic acid and glycols. Or, a polyester-based polymer obtained by ring-opening polymerization of lactones; a (meth) acrylic acid ester-based polymer obtained by radically polymerizing a monomer such as ethyl (meth) acrylate or butyl (meth) acrylate; (meth). ) A vinyl polymer obtained by radically polymerizing a monomer such as an acrylic acid ester-based monomer, vinyl acetate, acrylonitrile, or styrene; a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer; a polysulfide-based polymer. Nylon 6. Nylon 11 by ring-open polymerization of ε-aminolaurolactum, polyamide-based polymer such as copolymerized nylon having two or more components of the above-mentioned nylon; for example, depolymerized from bisphenol A and carbonyl chloride. Examples thereof include the produced polycarbonate-based polymer and diallyl phthalate-based polymer.

Saturated hydrocarbon-based polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers have a relatively low glass transition temperature, and the obtained cured product. Is more preferable because it has excellent cold resistance.

The glass transition temperature of the organic polymer as the component (B) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower. .. If the glass transition temperature exceeds 20 ° C., the viscosity in winter or cold regions may increase and workability may deteriorate, and the flexibility of the cured product may decrease and the elongation may decrease. The glass transition temperature can be determined by DSC measurement.

Organic polymers such as saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth) acrylic acid ester-based polymers are adhesive groups of low molecular weight components when used as a base polymer for adhesives and sealants. It is preferable because there is little contamination due to transfer to materials.

Further, the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer are particularly preferable because they have high moisture permeability and are excellent in deep curability and also excellent adhesiveness when made into a one-component composition. The polyoxyalkylene polymer is most preferable. Among the polyoxyalkylene-based polymers, the polyoxypropylene-based polymer is particularly preferable.

(Polyoxyalkylene polymer)
The polyoxyalkylene polymer is essentially a general formula (3):
-R ⁵ -O- ··· (3)
A polymer having a repeating unit represented by (R ⁵ is a linear or branched alkylene group having 1 to 14 carbon atoms), and is represented by the general formula (3) in all the repeating units of the polymer. It is preferable that the repeating unit to be subjected to is 50% by weight or more. R ⁵ in the general formula (3) is a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (3) are −CH ₂ O−, −CH ₂ CH ₂ O−, −CH ₂ CH ₂ CH ₂ O−, −CH ₂ CH (CH ₃ ) O−. , -CH ₂ CH (C ₂ H ₅ ) O-, -CH ₂ C (CH ₃ ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, and the like. The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. In particular, when it is used as a sealing material or the like, it is preferable that the polymer composed of a propylene oxide polymer as a main component is amorphous and has a relatively low viscosity.

Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organic aluminum compound shown in JP-A-61-215623 with porphyrin. Transition Metal Compound-Porphyrin Complex Catalyzed Polymerization Method, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent No. 3278457, US Patent No. 3278458, US Patent No. 3278459, US Patent No. 3427256, US Patent No. 3427334, Polymerization method using a composite metal cyanide complex catalyst shown in US Pat. No. 3,427,335, polymerization method using a catalyst composed of a polyphosphazene salt exemplified by JP-A-10-273512, phosphazene exemplified by JP-A-11-060722 Examples thereof include a polymerization method using a catalyst composed of a compound, but the present invention is not particularly limited.

Methods for producing a polyoxyalkylene polymer having a reactive silyl group are described in Japanese Patent Publication No. 45-363319, No. 46-12154, Japanese Patent Application Laid-Open No. 50-156599, No. 54-6096, No. 55-13767, The ones proposed in the publications such as 55-13468, 57-164123, 5-2450, US Patent 363255, US Patent 4345053, US Patent 4366307, US Patent 4960844, etc., and JP-A-61. -197631, 61-215622, 61-215623, 61-218632, Japanese Patent Application Laid-Open No. 3-72527, Japanese Patent Application Laid-Open No. 3-47825, Japanese Patent Application Laid-Open No. 8-231707. Examples thereof include polyoxyalkylene-based polymers having a number average molecular weight of 6,000 or more, a high molecular weight of Mw / Mn of 1.6 or less, and a narrow molecular weight distribution, but are not particularly limited thereto.

The polyoxyalkylene polymer having a reactive silyl group may be used alone or in combination of two or more.

(Saturated hydrocarbon polymer)
The saturated hydrocarbon-based polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer forming the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. An olefin compound having 2 to 6 carbon atoms such as the above is polymerized as a main monomer, (2) a diene compound such as butadiene, isoprene, etc. is independently polymerized, or the olefin compound is copolymerized. After that, it can be obtained by a method such as hydrogenation. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because they can easily introduce functional groups at the ends, easily control the molecular weight, and can increase the number of terminal functional groups, and isobutylene-based polymers are particularly preferable. preferable.

Those whose main chain skeleton is a saturated hydrocarbon-based polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture blocking property.

The isobutylene-based polymer may be formed of all the monomer units from the isobutylene units or may be a copolymer with other monomers, but contains 50% by weight or more of the repeating units derived from isobutylene from the viewpoint of rubber properties. It is preferable that the polymer contains 80% by weight or more, and 90% by weight to 99% by weight is particularly preferable.

Various polymerization methods have been conventionally reported as methods for synthesizing saturated hydrocarbon-based polymers, but in particular, many so-called living polymerization methods have been developed in recent years. In the case of saturated hydrocarbon-based polymers, especially isobutylene-based polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1977, Vol. 15, 2869. It is known that it can be easily produced by using (page), a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends. ing.

Examples of the method for producing a saturated hydrocarbon polymer having a reactive silyl group include JP-A-4-69659, JP-A-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-64-2904. It is described in each specification of Kaihei 1-197509, Patent Gazette No. 2539445, Patent Gazette No. 2873395, JP-A-7-53882, etc., but is not particularly limited thereto.

The saturated hydrocarbon-based polymer having the reactive silyl group may be used alone or in combination of two or more.

((Meta) acrylic acid ester polymer)
When the organic polymer (B) having a reactive silyl group at the end of the molecular chain is a (meth) acrylic acid ester-based polymer, the (meth) acrylic acid ester-based polymer is the above-mentioned general formula (1). ) Is a (meth) acrylic acid ester-based polymer having a reactive silyl group at the end of the molecular chain other than the (meth) acrylic acid ester-based polymer (A) having a reactive silyl group at the end of the main chain. All you need is. That is, in the (meth) acrylic acid ester-based polymer as the organic polymer (B) having a reactive silyl group at the end of the molecular chain, the silicon atom of the reactive silyl group is bonded to the α-position of the electron-withdrawing group, and , It does not have to be a (meth) acrylic acid ester-based polymer having a reactive silyl group having a monofunctional monoalkoxysilyl group.

Therefore, if the silicon atom of the reactive silyl group of the (meth) acrylic acid ester-based polymer as the organic polymer (B) is not bonded to the α-position of the electron-withdrawing group, the reactive silyl group may be monofunctional. It may be bifunctional or trifunctional, and is not particularly limited as long as it is a reactive silyl group represented by the general formula (2). When the reactive silyl group of the (meth) acrylic acid ester-based polymer as the organic polymer (B) is not a monofunctional monoalkoxysilyl group, the silicon atom of the reactive silyl group is α of the electron-withdrawing group. It may be bound to any of the position, β position, γ position and the like.

The reactive silyl group of the (meth) acrylic acid ester-based polymer as the organic polymer (B) is, for example, a dialkoxysilyl group or a trialkoxysilyl group, and the silicon atom of the reactive silyl group is an electron-withdrawing group. It is bound to the β-position or γ-position of.

The (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer is not particularly limited, and various ones can be used. For example, 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) acrylic acid 2-aminoethyl, (meth) acrylic acid (3-trimethoxysilyl) propyl, (meth) acrylic acid (3-dimethoxymethylsilyl) propyl, (meth) acrylic Acid (2-trimethoxysilyl) ethyl, (meth) acrylic acid (2-dimethoxymethylsilyl) ethyl, (meth) acrylic acid trimethoxysilylmethyl, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic Ethylene oxide adduct of acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoro (meth) acrylate Ethyl-2-perfluorobutylethyl, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl (meth) acrylate (Meta) acrylics such as -2-perfluoroethyl ethyl, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, etc. Examples thereof include acid ester-based monomers.

In the (meth) acrylic acid ester-based polymer, the following vinyl-based monomers can be copolymerized together with the (meth) acrylic acid ester-based monomer. Examples of the vinyl-based monomer are styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; 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 fumaric acid, fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, Maleimide-based monomers such as dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl-based monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl acetate and vinyl propionate , Vinyl esters such as vinyl pivalate, vinyl benzoate, vinyl cinnate; alkens such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. ..

These may be used alone, or a plurality of them may be copolymerized. Of these, a copolymer composed of a styrene-based monomer and a (meth) acrylic acid ester-based monomer is preferable from the viewpoint of physical properties of the product. A (meth) acrylic acid ester-based polymer composed of an acrylic acid ester-based monomer and / or a methacrylic acid ester-based monomer is more preferable, and an acrylic acid ester-based polymer composed of an acrylic acid ester-based monomer is particularly preferable.

Butyl acrylate-based monomers are more preferable because they are required to have physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, and heat resistance in applications such as general construction. On the other hand, in applications such as automobiles where oil resistance is required, a copolymer composed of a monomer mainly composed of ethyl acrylate is more preferable. This copolymer composed of a monomer mainly composed of ethyl acrylate has excellent oil resistance, but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is used. It can also be replaced with butyl acrylate. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less by weight, and further 30 More preferably, it is less than%.

It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the alkyl group of the side chain in order to improve low temperature characteristics without impairing oil resistance. However, since the heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less by weight.

It is possible to obtain a suitable polymer by changing the monomer ratio in consideration of the required physical properties such as oil resistance, heat resistance, and low temperature characteristics according to various uses and required purposes. For example, although not limited, an example having an excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics is ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 by weight). ~ 30/30 ~ 20) copolymers can be mentioned. In the present invention, these preferred monomers may be copolymerized with other monomers, or even block copolymerized, in which case, it is preferable that these preferred monomers are contained in an amount of 40% or more by weight. ..

(Synthesis method of (meth) acrylic acid ester polymer)
The method for synthesizing the (meth) acrylic acid ester-based polymer is not particularly limited, and a known method may be used. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator has a problem that the value of the molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. There is. Therefore, in order to obtain a (meth) acrylic acid ester-based polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the end of the molecular chain at a high proportion, it is necessary to obtain a (meth) acrylic acid ester-based polymer. , It is preferable to use a living radical polymerization method that does not use a non-nitrile-based azo-based polymerization initiator or an organic peroxide-based polymerization initiator.

Among the "living radical polymerization methods", the "atomic transfer radical polymerization method" for polymerizing a (meth) acrylic acid ester-based monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is described above. In addition to the characteristics of the "living radical polymerization method", it has a specific functional group because it has a halogen or the like at the end, which is relatively advantageous for the functional group conversion reaction, and the degree of freedom in designing the initiator and catalyst is large (). It is more preferable as a method for producing a meta) acrylic acid ester-based polymer. Examples of this atom transfer radical polymerization method include the methods described in Mattyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc), 1995, Vol. 117, p. 5614.

As a method for producing a (meth) acrylic acid ester-based polymer having a reactive silyl group, for example, chain transfer to JP-A-3-14068, JP-A-4-55444, JP-A-6-21922, etc. A production method using a free radical polymerization method using an agent is disclosed. Further, JP-A-9-272714 and the like disclose a production method using an atom transfer radical polymerization method, but the present invention is not particularly limited thereto. The (meth) acrylic acid ester-based polymer having a reactive silyl group may be used alone or in combination of two or more.

These organic polymers having a reactive silyl group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a reactive silyl group, a saturated hydrocarbon polymer having a reactive silyl group, and a (meth) acrylic acid ester polymer having a reactive silyl group. An organic polymer obtained by blending two or more kinds selected from the above can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid ester polymer having a reactive silyl group is described in JP-A-59-122541. It has been proposed in Kaisho 63-112642, JP-A-6-172631, JP-A-11-116763, etc., but is not particularly limited thereto. A preferred embodiment has a reactive silyl group and the molecular chain is substantially the following general formula (4):
-CH _2- C (R ⁶ ) (COOR ⁷ ) -... (4)
(R ⁶ indicates a hydrogen atom or a methyl group, R ⁷ indicates an alkyl group having 1 to 8 carbon atoms), and a (meth) acrylic acid ester monomer unit having an alkyl group having 1 to 8 carbon atoms. The following general formula (5):
-CH _2- C (R ⁶ ) (COOR ⁸ ) -... (5)
(R ⁶ is the same as above, R ⁸ is an alkyl group having 9 or more carbon atoms), and is a copolymer composed of (meth) acrylic acid ester monomer units having an alkyl group having 9 or more carbon atoms. , A method for producing by blending a polyoxyalkylene polymer having a reactive silyl group.

The ^{R 7} in the general formula (4), for example, a methyl group, an ethyl group, a propyl group, n- butyl group, t- butyl group, a 2-ethylhexyl group 1 to 8 carbon atoms such as, preferably from 1 4, more preferably 1 or 2 alkyl groups. The alkyl group of R ⁷ may be used alone or in combination of two or more.

The R ⁸ in the general formula (5), for example, nonyl, decyl, lauryl, tridecyl, cetyl group, stearyl group, having 9 or more carbon atoms such as behenyl groups, usually from 10 30, preferably Examples include 10 to 20 long chain alkyl groups. As in the case of R ⁷ , the alkyl group of R ⁸ may be used alone or in combination of two or more.

The molecular chain of the (meth) acrylic acid ester-based polymer is substantially composed of the monomer units of the general formula (4) and the general formula (5), and the term "substantially" as used herein means in the copolymer. It means that the total of the monomer units of the general formula (4) and the general formula (5) present in is more than 50% by weight. The total of the monomer units of the general formula (4) and the general formula (5) is preferably 70% by weight or more.

The abundance ratio of the monomer unit of the general formula (4) to the monomer unit of the general formula (5) is preferably 95: 5 to 40:60 by weight, and more preferably 90:10 to 60:40.

Examples of the monomer unit other than the general formula (4) and the general formula (5) that may be contained in the copolymer include acrylic acids such as acrylic acid and methacrylic acid; acrylamide, methacrylicamide, and N-methylolacrylamide. , Monomers containing amide groups such as N-methylolmethacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, Monomer units derived from alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like can be mentioned.

Organic polymers obtained by blending a saturated hydrocarbon-based polymer having a reactive silyl group and a (meth) acrylic acid ester-based polymer having a reactive silyl group are JP-A-1-1687664 and JP-A-2000-186176. Although it is proposed in the publication, etc., it is not particularly limited to these.

Further, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based polymer having a reactive silyl group, there is another method (meth) in the presence of an organic polymer having a reactive silyl group. ) A method of polymerizing an acrylic ester-based monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, and the like. It is not limited to these.

On the other hand, the main chain skeleton of the organic polymer B may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

The urethane bond component is not particularly limited, and examples thereof include a group generated by the reaction of an isocyanate group and an active hydrogen group (hereinafter, also referred to as an amide segment).

The amide segment has the general formula (6):
−NR ⁹ −C (= O) − ··· (6)
It is a group represented by (R ⁹ represents an organic group or a hydrogen atom). The organic group of R ⁹ is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms. It is a group represented by). Since this structure has a relatively high polarity, the strength of the cured product and the adhesiveness to the substrate tend to be high, which is desirable.

A cured product obtained by curing a curable composition composed of a polymer containing a urethane bond or an ester bond in the main chain may cause the main chain to cleave at the urethane bond or ester bond portion due to heat or the like, and the strength of the cured product. May decrease significantly.

If there are many amide segments in the main chain skeleton of the organic polymer (B), the viscosity of the polymer tends to increase. In addition, the viscosity may increase after storage, which may reduce the workability of the obtained composition. Further, as described above, the amide segment may be cleaved by heat or the like. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferable that the composition contains substantially no amide segment. On the other hand, the amide segment in the main clavicle of the organic polymer (B) tends to improve the curability. Therefore, when the main chain skeleton of the organic polymer (B) contains amide segments, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 3. Is particularly preferable. If the number is less than 1, the curability may not be sufficient, and if the number is larger than 10, the polymer may become highly viscous and difficult to handle.

Specifically, the amide segment is a urethane group formed by a reaction between an isocyanate group and a hydroxy group; a urea group formed by a reaction between an isocyanate group and an amino group; and a urea group formed by a reaction between an isocyanate group and a mercapto group. A thiourethane group and the like can be mentioned. Further, in the present embodiment, the group of the general formula (6) is also included in the group in which the urethane group, the urea group, and the active hydrogen in the thiourethane group are further reacted with the isocyanate group.

To exemplify an industrially easy method for producing an organic polymer (B) having an amide segment and a reactive silyl group, an excess polyisocyanate compound is reacted with an organic polymer having an active hydrogen-containing group at the terminal. After making a polymer having an isocyanate group at the end of the polyurethane-based main chain, or at the same time, the general formula (7)::
Z-R ^10- SiR ⁴ _3-a X _a ... (7)
(R ⁴ , X, a are the same as above. R ¹⁰ is a divalent organic group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxy group, a carboxy group, a mercapto group and Examples thereof include those produced by a method of reacting the Z group of a silicon compound represented by an amino group (which is an active hydrogen-containing group selected from the primary or secondary). Examples of known production methods for organic polymers related to this production method include Japanese Patent Application Laid-Open No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), and Japanese Patent Application Laid-Open No. 62. -13430 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), Japanese Patent Application Laid-Open No. 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21179 (US Pat. Japanese Patent No. 5364955), Japanese Patent Application Laid-Open No. 10-53637 (US Pat. , US Pat. No. 4,607,844, US Pat. No. 3,711,445, Japanese Patent Application Laid-Open No. 2001-323040 and the like.

Further, an organic polymer having an active hydrogen-containing group at the terminal has a general formula (8):
O = C = N-R ^10- SiR ⁴ _3-a X _a ... (8)
Examples thereof include those produced by reacting the reactive silyl group-containing isocyanate compound represented by (R ¹⁰ , R ⁴ , X and a are the same as described above). Examples of known production methods of the organic polymer (B) related to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A-2000-119365 (US Pat. No. 6,046,270), and JP-A. 1983-29818 (US Pat. No. 4345053), Japanese Patent Application Laid-Open No. 3-47825 (US Pat. No. 5068304), Japanese Patent Application Laid-Open No. 11-60724, Japanese Patent Application Laid-Open No. 2002-155145, Japanese Patent Application Laid-Open No. 2002-249538, WO 03/018658, WO 03/059981 and the like can be mentioned.

Examples of the organic polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer (polyether polyol) having a hydroxy group at the end, a polyacrylic polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxy group at the end (. Polyester polyol), polythiol compounds, polyamine compounds and the like. Among these, polyether polyols, polyacrylic polyols, and polyolefin polyols are preferable because the glass transition temperature of the obtained organic polymer is relatively low and the obtained cured product has excellent cold resistance. In particular, the polyether polyol is particularly preferable because the viscosity of the obtained organic polymer is low, the workability is good, and the deep curability and the adhesiveness are good. Further, the polyacrylic polyol and the saturated hydrocarbon-based polymer are more preferable because the cured product of the obtained organic polymer has good weather resistance and heat resistance.

As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxy groups per molecular end on average in all molecules are preferable. Specifically, the initiator, such as an oxyalkylene polymer, a composite metal cyanide complex and / or a polyhydroxy compound having at least two hydroxy groups, produced using a conventional alkali metal catalyst. Examples thereof include an oxyalkylene polymer produced by reacting an alkylene oxide.

Among the above-mentioned polymerization methods, the polymerization method using a composite metal cyanide complex has a lower degree of unsaturation, a narrower Mw / Mn, a lower viscosity, and a high acid resistance and a high weather resistance. It is preferable because it is possible to obtain coalescence.

Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxy group in the molecule. As a method for synthesizing this polymer, the living radical polymerization method is preferable because the molecular weight distribution is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable. Further, it is preferable to use a polymer obtained by continuous bulk polymerization of the acrylic acid alkyl ester-based monomer described in JP-A-2001-207157 at high temperature and high pressure by a so-called SGO process. Specific examples thereof include Alfon UH-2000 manufactured by Toagosei Co., Ltd.

Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (toluene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. ..

The silicon compound of the general formula (7) is not particularly limited, but specific examples thereof include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and (N-). Amino such as phenyl) -γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; and the like. Further, JP-A-6-21179 (US Patent No. 5364955), JP-A-10-53637 (US Pat. No. 5,756751), JP-A-10-204144 (EP0831108), JP-A-2000-169544, JP-A-2000-169545. As described in No., a Michael addition reaction product of various α, β-unsaturated carbonyl compounds and a primary amino group-containing silane, or various (meth) acryloyl group-containing silanes and a primary amino group-containing compound. The Michael addition reaction product of the above can also be used as the silicon compound of the general formula (7).

The reactive silyl group-containing isocyanate compound of the general formula (8) is not particularly limited, but specific examples thereof include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-Methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like. Further, as described in Japanese Patent Application Laid-Open No. 2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of the general formula (7) with an excess of the polyisocyanate compound is also a general formula. It can be used as the reactive silyl group-containing isocyanate compound of (8).

[3. Curable composition]
The curable composition according to one embodiment of the present invention includes the (meth) acrylic acid ester-based polymer (A) (hereinafter, may be simply referred to as “component (A)” in the present specification) and the above. It contains an organic polymer (B) having a reactive silyl group at the end of the molecular chain (hereinafter, may be simply referred to as “component (B)” in the present specification).

The number of parts of the component (A) in the curable composition according to the embodiment of the present invention is preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight with respect to 100 parts by weight of the component (B). It is by weight, more preferably 15 to 150 parts by weight, and even more preferably 20 to 100 parts by weight. If it is 5 parts by weight or more, the weather resistance can be improved while increasing the elongation of the cured product, and if it is 500 parts by weight or less, the elongation property of the cured product is good, which is preferable.

[3.1. Additive〕
The curable composition according to one embodiment of the present invention may contain a component (A) and a component (B), but in addition to the components (A) and (B), a catalyst, a plasticizer, and heat Expandable fine-grained hollow body, adhesive-imparting agent, antioxidant, light stabilizer, ultraviolet absorber, filler, silicate, physical property adjusting agent, thixo property-imparting agent, epoxy group-containing compound, photocurable substance, oxygen It may contain additives such as curable substances, flame retardants and solvents.

(catalyst)
A silanol condensation catalyst can be used in the curable composition according to one embodiment of the present invention. Preferred examples of the silanol condensation catalyst include a tin-based catalyst, preferably an organic tin-based curing catalyst. Specific examples of the organotin catalyst include dimethyl tin diacetate, dimethyl tin bis (acetylacetonate), dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin phthalate, dibutyl tin dioctanoate, and dibutyl tin bis (2-ethylhexanoate). ), Dibutyl tin bis (methyl maleate), dibutyl tin bis (ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin Bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonylphenoxide), dibutenyl tin oxide, dibutyl tin oxide , Dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, dioctyltin dilaurate, dioctyltindi Tetravalent organic tin compounds such as acetate and dioctyl tin bis (acetylacetonate); divalent tin such as tin octylate and tin versaticate can be mentioned, but are not limited thereto. Of these, dibutyltin bis (acetylacetonate) or tin octylate is preferable from the viewpoint of curability.

Curing catalysts other than the above-mentioned organotin-based catalysts can also be used. Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonate) diisopropoxytitanium, and diisopropoxytitanium bis (ethylacetatete); aluminum tris. Organic aluminum compounds such as (acetylacetonate), aluminum tris (ethylacetacetate), diisopropoxyaluminum ethylacetacetate; zirconium compounds such as zirconite tetrakis (acetylacetonate). A carboxylic acid and / or a metal carboxylic acid salt can also be used as a curing catalyst. Further, an amidine compound as described in WO2008 / 078654 can also be used. Examples of amidine compounds are 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo [4.4]. .0] Deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene and the like can be mentioned, but are not limited thereto.

The amount of the catalyst used is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 0.2 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is 0.3 to 5 parts by weight. This is because if it is less than 0.1 part by weight, appropriate curability is not exhibited, and if it exceeds 10 parts by weight, curing is too fast, an appropriate cured product cannot be formed, and desired performance cannot be sufficiently exhibited.

(Plasticizer)
A plasticizer may be used in the curable composition according to one embodiment of the present invention. Examples of plasticizers include non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyllicylinate; tricres. Phosphate esters such as zir phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxy stearic acid Examples thereof include epoxy plasticizers such as benzyl acid.

In addition, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate , Phthalate esters such as diisoundecyl phthalate and bisbutylbenzyl phthalate can also be used, but in consideration of the influence on the human body and the environment, it is preferable that the amount of these phthalates used is small, and it is desirable not to use them. When phthalates are used, diisodecyl phthalate or diisoundecyl phthalate is preferable, and diisodecyl phthalate is more preferable. In addition, cyclohexanedicarboxylate obtained by adding the above-mentioned phthalates with water can be used without worrying about safety. This plasticizer is sold by BASF under the trade name Hexamol DINCH and is easily available.

Since the relatively low molecular weight plasticizers mentioned above may contaminate the surrounding substrate on which the curable composition is applied, it is desirable that the amount used is small. In particular, porous stones tend to be contaminated, and granite, marble, siding boards, and the like are prone to seepage of plasticizer, which may spoil the aesthetic appearance. In order to suppress such deterioration of aesthetics, the amount of a low molecular weight plasticizer such as a phthalate ester plasticizer used is 200% by weight based on 100 parts by weight of the total amount of the components (A) and (B). It is less than or equal to parts, preferably 100 parts by weight or less, more preferably 70 parts by weight or less, and even more preferably 50 parts by weight or less. If it is desired to obtain a curable composition that does not cause contamination, it is most desirable to use no low molecular weight plasticizer at all.

When the paint is applied onto the curable composition, it is preferable to use a phthalate ester plasticizer in combination as long as the stainability is not reduced. This is because when used in combination, the adhesion of the coating film is improved and the problem of peeling can be improved. Specifically, 1 part by weight to 80 parts by weight is preferable, 2 parts by weight to 75 parts by weight is more preferable, and 3 parts by weight to 70 parts by weight is preferable with respect to 100 parts by weight of the total amount of the components (A) and (B). Most preferred.

In addition, a polymer plasticizer can be used in the curable composition according to the embodiment of the present invention. When a high molecular plasticizer is used, the initial physical properties of the obtained cured product are maintained for a long period of time as compared with the case where a low molecular plasticizer which is a plasticizer containing no polymer component in the molecule is used. Further, the drying property (also referred to as coating property) when the alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester-based plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and divalent alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; Is a polyether polyol such as 1,000 or more polyethylene glycols, polypropylene glycols, polytetramethylene glycols, or polyethers such as derivatives obtained by converting the hydroxy group of these polyether polyols into an ester group, an ether group, etc .; polystyrene, poly- Polystyrenes such as α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like, but are not limited thereto.

Among these polymer plasticizers, those that are compatible with the polymers of the components (A) and (B) are preferable. From this point of view, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, surface curability and deep curability are improved, and curing delay after storage does not occur, so that it is preferable, and polypropylene glycol is more preferable. Further, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among the vinyl-based polymers, acrylic-based polymers and / or methacrylic-based polymers are preferable, and acrylic-based polymers such as polyacrylic acid alkyl esters are more preferable. As a method for synthesizing this polymer, the living radical polymerization method is preferable because the molecular weight distribution is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable. Further, it is preferable to use a polymer obtained by continuous bulk polymerization of the acrylic acid alkyl ester-based monomer described in JP-A-2001-207157 at high temperature and high pressure by a so-called SGO process. This plasticizer is sold by Toagosei Co., Ltd. under the trade name of Alfon.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000. To 5,000, most preferably 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rainfall, the initial physical properties of the cured product cannot be maintained for a long period of time, and the alkyd coating property cannot be improved. On the other hand, if the molecular weight is too high, the viscosity becomes high and the workability deteriorates. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, preferably less than 1.80, more preferably 1.70 or less, still more preferably 1.60 or less, still more preferably 1.50 or less. It is particularly preferably .40 or less, and most preferably 1.30 or less.

The number average molecular weight is measured by the GPC method in the case of a vinyl polymer and by the end group analysis method in the case of a polyether polymer. The molecular weight distribution (Mw / Mn) is measured by the GPC method (polystyrene conversion).

The plasticizer may be used alone or in combination of two or more. Further, the low molecular weight plasticizer and the high molecular weight plasticizer may be used in combination. These plasticizers can also be blended during the production of the polymer.

The amount of the high molecular weight plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is from parts by weight to 100 parts by weight, and even more preferably from 20 parts by weight to 50 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

(Heat-expandable fine-grained hollow body)
Further, in the curable composition according to one embodiment of the present invention, the heat-expandable fine-grained hollow body described in JP-A-2004-51701 or JP-A-2004-66749 can be used. The heat-expandable fine-grained hollow body is a polymer outer shell material (vinylidene chloride-based copolymer, acrylonitrile-based copolymer, or vinylidene chloride-acrylonitrile copolymer) containing a low-boiling compound such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape (coalescence). By heating the adhesive portion using the curable composition according to the embodiment of the present invention, the gas pressure in the shell of the heat-expandable fine-grained hollow body is increased, and the polymer outer shell material is softened to increase the volume. It expands dramatically and serves to peel off the adhesive interface. By using the heat-expandable fine-grained hollow body, it is possible to obtain an adhesive composition which can be easily peeled off without breaking the material by simply heating it when it is not needed, and which can be peeled off by heat without using any organic solvent.

(Adhesive imparting agent)
Aminosilane can be used in the curable composition according to one embodiment of the present invention. Aminosilane is a compound having a reactive silyl group and an amino group in the molecule, and is usually referred to as an adhesive-imparting agent. By using this, it can be used for various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene and polycarbonate. When used, it exhibits a remarkable adhesiveness improving effect under non-primer conditions or primer-treated conditions. When used under non-primer conditions, the effect of improving the adhesiveness to various adherends is particularly remarkable. Aminosilane is another compound that can function as a physical property adjusting agent, a dispersibility improving agent for an inorganic filler, and the like.

Reactive of Aminosilane As a specific example of the reactive group of the silyl group, the groups already exemplified can be mentioned, but a methoxy group, an ethoxy group and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more. Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ. -(2-Aminoethyl) Aminopropyltrimethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldimethoxysilane, γ- (2-Aminoethyl) Aminopropyltriethoxysilane, γ- (2-Aminoethyl) Amino Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- [2- (2-aminoethyl) aminoethyl] aminopropyltrimethoxysilane, γ- (6-aminohexyl) amino Propyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltri Amino group-containing silanes such as methoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) ) -3- (Triethoxysilyl) -1-propaneamine and other ketimine-type silanes can be mentioned.

Of these, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane are used to ensure good adhesion. preferable. Only one type of aminosilane may be used, or two or more types may be used in combination. It has been pointed out that γ- (2-aminoethyl) aminopropyltrimethoxysilane is more irritating than other aminosilanes, and instead of reducing the amount of this aminosilane, γ-aminopropyltrimethoxysilane should be used in combination. Can alleviate irritation.

The blending amount of aminosilane is preferably about 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, still more preferably 2 to 5 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). preferable. If the blending amount of aminosilane is less than 1 part by weight, sufficient adhesiveness may not be obtained. On the other hand, if the blending amount exceeds 20 parts by weight, the cured product becomes brittle and sufficient strength cannot be obtained, and the curing rate may slow down.

An adhesive imparting agent other than aminosilane can be used in the curable composition according to the embodiment of the present invention. Specific examples of the adhesive imparting agent other than aminosilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4-). Epoxy group-containing silanes such as epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyl Isocyanate group-containing silanes such as methyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy Mercapt group-containing silanes such as silane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxy) Carboxysilanes such as ethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanuratesilanes such as tris (trimethoxysilyl) isocyanurate. it can. Further, a condensate obtained by partially condensing the above silanes can also be used. Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters and the like, which are modified derivatives of these, can also be used as adhesive imparting agents. ..

The effects of the adhesive-imparting agent used in the curable composition according to one embodiment of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper and mortar, and vinyl chloride. When used on organic substrates such as acrylic, polyester, polyethylene, polypropylene, and polycarbonate, it exhibits a remarkable adhesiveness improving effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the adhesiveness to various adherends is particularly remarkable. Specific examples other than the adhesive-imparting agent described above are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like. The adhesiveness-imparting agent may be used alone or in combination of two or more. By using these adhesive-imparting agents, the adhesiveness to the adherend can be improved.

Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferable in order to ensure good adhesiveness.

The amount of the adhesive-imparting agent used is preferably about 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). About 1 part by weight is more preferable, and about 1 to 7 parts by weight is particularly preferable. If the blending amount of the adhesiveness-imparting agent is less than this range, sufficient adhesiveness may not be obtained. On the other hand, if the blending amount of the adhesive-imparting agent exceeds this range, practical deep curability may not be obtained.

As described above, an epoxy resin can also be used as the adhesiveness imparting agent. However, since the epoxy resin may reduce the catalytic activity depending on the amount used, it is preferable that the amount of the epoxy resin used is small in the curable composition according to the embodiment of the present invention. The amount of the epoxy resin used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially contained in an amount of 100 parts by weight based on the total amount of the components (A) and (B). Not particularly preferred.

(Antioxidant)
An antioxidant (anti-aging agent) can be used in the curable composition according to the embodiment of the present invention. The heat resistance of the cured product can be increased by using an antioxidant. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, but hindered phenols are particularly preferable. Similarly, Tinubin 622LD, Tinubin 144, CHIMASSORB944LD, CHIMASORB119FL (all manufactured by BASF Japan Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all of which are above). Also manufactured by ADEKA CORPORATION; Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.). A hindered amine-based light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is a part by weight.

(Light stabilizer)
A light stabilizer can be used in the curable composition according to one embodiment of the present invention. The use of a light stabilizer can prevent photooxidation deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, but hindered amine-based compounds are particularly preferable. The amount of the light stabilizer used is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is a part by weight. Specific examples of the light stabilizer are also described in JP-A-9-194731.

When a photocurable substance is used in combination with the curable composition according to an embodiment of the present invention, particularly when an unsaturated acrylic compound is used, hindered amine-based photostable as described in JP-A-5-70531. It is preferable to use a tertiary amine-containing hindered amine-based light stabilizer as the agent for improving the storage stability of the composition. As hindered amine-based light stabilizers containing tertiary amines, chinubin 622LD, chinubin 144, CHIMASORB119FL (all manufactured by BASF Japan Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (all of which are stocks). (Manufactured by ADEKA Corporation); Light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by BASF Japan Ltd.) can be exemplified.

(UV absorber)
An ultraviolet absorber can be used in the curable composition according to one embodiment of the present invention. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is a part by weight. It is preferable to use a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber in combination.

(filler)
A filler can be used in the curable composition according to one embodiment of the present invention. Fillers include fumed silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic anhydride, hydrous silicic acid, and reinforcing fillers such as carbon black; heavy calcium carbonate, calcium glue carbonate, carbon dioxide. Magnesium, Keisou soil, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, active zinc white, silas balloon, glass microballoon, phenol resin and chloride Fillers such as resin powders such as organic microballoons of vinylidene resin, PVC powder, PMMA powder; and fibrous fillers such as glass fibers and filaments can be mentioned. When a filler is used, the amount used is 1 part by weight to 250 parts by weight, preferably 10 parts by weight to 200 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B).

When it is desired to obtain a cured product having high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic acid anhydride, hydrous silicic acid, carbon black, and surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, active zinc flower, etc. is preferable, and the total amount of the components (A) and (B) is in the range of 1 part to 250 parts by weight with respect to 100 parts by weight. When used, favorable results are obtained, more preferably 1 part by weight to 200 parts by weight, further preferably 50 parts by weight to 200 parts by weight, and even more preferably 80 parts by weight to 200 parts by weight. If you want to obtain a cured product with low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and silas balloon. When the filler selected from the above is used in the range of 5 parts by weight to 200 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B), preferable results can be obtained. In general, the larger the specific surface area value of calcium carbonate, the greater the effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use both surface-treated fine calcium carbonate and calcium carbonate having a large particle size such as heavy calcium carbonate. The particle size of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid and / or a fatty acid salt. Further, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and one that has not been surface-treated can be used.

In the curable composition according to one embodiment of the present invention, it is preferable to use an organic balloon or an inorganic balloon in order to improve the workability (sharpness or the like) of the curable composition and to make the surface of the cured product matte. These fillers can be surface-treated, only one type may be used, or two or more types may be mixed and used. In order to improve workability (sharpness, etc.), the particle size of the balloon is preferably 0.1 mm or less. In order to make the surface of the cured product matte, the particle size of the balloon is preferably 5 μm to 300 μm.

The curable composition according to one embodiment of the present invention has good chemical resistance to the cured product, and therefore, siding boards, especially ceramic siding boards, etc. It is preferably used as an adhesive for outer wall tiles and the adhesive remains on the joints as it is, but it is desirable that the design of the outer wall and the design of the sealing material are in harmony. In particular, as the outer wall, a high-class outer wall has come to be used due to spatter coating, coloring aggregate, and the like. When a curable composition according to an embodiment of the present invention contains a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 mm to 5.0 mm, the cured product is such. It harmonizes with the luxurious outer wall and has excellent chemical resistance. Therefore, the obtained cured product has an excellent curable composition that lasts for a long period of time. When a granular substance is used, the surface has a sand-like or sandstone-like graininess, and when a scaly substance is used, the surface becomes uneven due to the scaly shape.

Preferred diameters, blending amounts, materials and the like of the scaly or granular substance are as follows as described in JP-A-9-53063.

The diameter is 0.1 mm or more, preferably about 0.1 mm to 5.0 mm, and an appropriate size is used according to the material, pattern, etc. of the outer wall. Those having a diameter of about 0.2 mm to 5.0 mm or 0.5 mm to 5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 mm to 1.00 mm). The scaly or granular substance is premixed in the sealing main material and transported to the construction site as a sealing material, or is mixed in the sealing main material at the construction site during use.

The scaly or granular substance is 1 part to 200 parts by weight based on 100 parts by weight of the composition such as the sealant composition and the adhesive composition, or 100 parts by weight of the total amount of the components (A) and (B). About parts by weight are mixed. The blending amount is appropriately selected according to the size of each scaly or granular substance, the material of the outer wall, the pattern, and the like.

As the scaly or granular substance, natural products such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. The curable composition according to the present embodiment is colored in an appropriate color according to the material, pattern, etc. of the outer wall in order to enhance the design when the joint portion is filled.

Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the obtained cured product has a sand-like or sandstone-like grainy surface, and the weight is reduced. Can be planned. The preferable diameter, blending amount, material and the like of the balloon are as follows as described in JP-A-10-251618.

The balloon is a spherical filler having a hollow inside. Examples of the material of this balloon include, but are not limited to, inorganic materials such as glass, silas, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran. , Inorganic materials and organic materials can be composited or laminated to form a plurality of layers. Inorganic, organic, or a combination of these balloons can be used. Further, as the balloon to be used, the same balloon may be used, or a plurality of types of balloons made of different materials may be mixed and used. Further, the balloon may be a balloon whose surface has been processed and / or coated, or a balloon whose surface has been treated with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface-treated with an adhesive-imparting agent.

In order to obtain a sand-like or sandstone-like grainy surface, the balloon preferably has a particle size of 0.1 mm or more. Those having a particle size of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm can also be used. If the particle size is less than 0.1 mm, even if a large amount is blended, the viscosity of the composition is only increased, and a grainy feeling may not be exhibited. The blending amount of the balloon can be easily determined depending on the degree of graininess of the target sandbox or sandstone tone. Usually, it is desirable to add a particle size of 0.1 mm or more in a volume concentration in the curable composition in the range of 5 vol% to 25 vol%. If the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and if it exceeds 25 vol%, the viscosity of the sealant or adhesive becomes high, workability is poor, and the modulus of the cured product becomes high, so that the sealant or adhesive becomes adhesive. The basic performance of the agent tends to be impaired. The volume concentration in which the balance with the basic performance of the sealing material is particularly preferable is 8 vol% to 22 vol%.

When a balloon is used, an anti-slip agent as described in JP-A-2000-154368 and a cured product as described in JP-A-2001-164237 are added to the uneven state to matte the surface. Amine compounds for the state, especially primary and / or secondary amines having a melting point of 35 ° C. or higher, can be used.

Specific examples of the balloon are JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, and JP-A-10. It is described in JP-A-251618, JP-A-2000-154368, JP-A-2001-164237, WO97 / 05201 and the like.

Even when the curable composition according to one embodiment of the present invention contains cured product particles of a sealing material, irregularities can be formed on the surface of the cured product to improve the design. Preferred diameters, blending amounts, materials and the like of the cured sealant particles are as follows as described in Japanese Patent Application Laid-Open No. 2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 mm to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber, and the like, and the material is not limited as long as it is used as a sealing material, but a modified silicone-based sealing material is preferable.

(Syricate)
Further, silicate can be used for the curable composition according to the embodiment of the present invention. This silicate acts as a cross-linking agent and has a function of improving the resilience, durability, and creep resistance of the polymer obtained by curing the components (A) and (B). Furthermore, it also has the effect of improving adhesiveness, water resistance, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partially hydrolyzed condensate thereof can be used. When silicate is used, the amount used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). is there.

Specific examples of silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-. Examples thereof include tetraalkoxysilanes (tetraalkylsilicates) such as butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

The partially hydrolyzed condensate of tetraalkoxysilane is more preferable because the effect of improving the recoverability, durability, and creep resistance of the obtained cured product is greater than that of tetraalkoxysilane.

Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to the tetraalkoxysilane by a usual method and partially hydrolyzing and condensing the tetraalkoxysilane. Further, as the partially hydrolyzed condensate of the organosilicate compound, a commercially available product can be used. Examples of such a condensate include methyl silicate 51 and ethyl silicate 40 (both manufactured by Corcote Co., Ltd.).

(Physical property adjuster)
In the curable composition according to one embodiment of the present invention, a physical property adjusting agent for adjusting the tensile properties of the cured product produced may be used, if necessary. The physical property adjusting agent is not particularly limited, but for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy. Alkylisopropenoxysilane such as silane, γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Alkoxysilanes having functional groups such as silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; silicone Alligators; polysiloxanes and the like can be mentioned. By using the physical property adjusting agent, the hardness of the curable composition according to the embodiment of the present invention when cured can be increased, or conversely, the hardness can be decreased to obtain elongation at break. The physical property adjusting agent may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has an action of lowering the modulus of the cured product without aggravating the stickiness of the surface of the cured product. In particular, compounds that produce trimethylsilanol are preferred. Examples of the compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis include the compounds described in JP-A-5-117521. Further, hexanol, octanol, a derivative of alkyl alcohol compound to produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol by hydrolysis of decanol, etc. are described in JP-A-11-241029 trimethylol propane, glycerine, hydroxy groups such as pentaerythritol or sorbitol may be mentioned a compound which forms a silicon compound that produces R ₃ SiOH such as trimethyl silanol a 3 or more polyhydric alcohol derivative by hydrolysis.

The can also include compounds that produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Further, a polymer having a crosslinkable reactive silyl group described in JP-A-6-279693 and a silicon-containing group that can become a monosilanol-containing compound by hydrolysis can also be used.

The physical property adjusting agent is used in the range of 0.1 parts by weight to 20 parts by weight, preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). To.

(Tixogenic agent)
In the curable composition according to one embodiment of the present invention, a ticking property-imparting agent (anti-dripping agent) may be used in order to prevent sagging and improve workability, if necessary. The anti-dripping agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when a rubber powder having a particle diameter of 10 μm to 500 μm as described in JP-A-11-349916 and an organic fiber as described in JP-A-2003-155389 are used, the thixophilicity is improved. A curable composition having high workability and good workability can be obtained. These thixophilic imparting agents (anti-dripping agents) may be used alone or in combination of two or more. The thixo-imparting agent is used in the range of 0.1 parts by weight to 20 parts by weight, preferably in the range of 1 part to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). To.

(Compound containing epoxy group)
In the curable composition according to one embodiment of the present invention, a compound containing an epoxy group in one molecule can be used. The use of a compound having an epoxy group can enhance the resilience of the cured product. Examples of the compound having an epoxy group include compounds such as epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and 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, Epoxy butyl steerate and the like can be mentioned. Of these, E-PS is particularly preferable. The epoxy compound is preferably used in the range of 0.5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B).

(Photocurable substance)
A photocurable substance can be used in the curable composition according to the embodiment of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a fairly short time due to the action of light, resulting in a physical change such as hardening. Many known compounds of this type include organic monomers, oligomers, resins, and compositions containing them, and any commercially available compound can be adopted. As a typical example, unsaturated acrylic compounds, vinyl polysilicate dermatates, azide resins and the like can be used. The unsaturated acrylic compound is a monomer having one or several acrylic or methacrylic unsaturated groups, an oligomer, or a mixture thereof, and is a propylene (or butylene, ethylene) glycol di (meth) acrylate or neopentyl. Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M. -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (polyfunctional) Aronix M-400 can be exemplified, but particularly containing an acrylic functional group. A compound containing 3 or more of the same functional groups on average in one molecule is preferable (all Aronix are products of Toagosei Co., Ltd.).

Examples of vinyl polysilicates include those obtained by esterifying polyvinyl alcohol with cinnamic acid, which is a photosensitive resin having a cinnamoyl group as a photosensitive group, and many vinyl polysilicate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group, and is usually a rubber photosensitive liquid to which a diazide compound is added as a photosensitive agent, as well as a "photosensitive resin" (March 17, 1972). (From pages 93 to 106 to 117), published by the Publishing Department of the Printing Society, and used alone or in combination with a sensitizer as needed. can do. In addition, the effect may be enhanced by adding a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine. The photocurable substance is used in the range of 0.1 parts by weight to 20 parts by weight, preferably 0.5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). If it is 0.1 parts by weight or less, there is no effect of increasing the weather resistance, and if it is 20 parts by weight or more, the cured product becomes too hard and tends to crack.

(Oxygen curable substance)
An oxygen-curable substance can be used in the curable composition according to one embodiment of the present invention. An example of an unsaturated compound that can react with oxygen in the air can be exemplified as an oxygen-curable substance. It reacts with oxygen in the air to form a cured film near the surface of the cured product, and the surface becomes sticky and the surface of the cured product becomes sticky. It acts to prevent the adhesion of dust and dirt. Specific examples of the oxygen-curable substance include dry oils such as diene oil and linseed oil, and various alkyd resins obtained by modifying the dry oils; acrylic copolymers modified with the dry oils and epoxy-based ones. Resin, silicon resin; 1,2-polybutadiene, 1,4-polybutadiene, polymer of C5 to C8 diene obtained by polymerizing or copolymerizing a diene compound such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers such as NBR and SBR obtained by copolymerizing the liquid polymer of No. 1 and monomers such as acrylonitrile and styrene having copolymerizability with these diene compounds so that the diene compound is the main component, and Examples thereof include various modified products (maleinized modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Of these, drilling oil and liquid diene-based polymers are particularly preferable. In addition, the effect may be enhanced by using a catalyst that promotes the oxidative curing reaction and / or a metal dryer in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. The amount of the oxygen-curable substance used is preferably in the range of 0.1 parts by weight to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and more preferably 0. It is 5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

(Flame retardants)
A phosphorus-based plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and heat-expandable graphite are added to the curable composition according to an embodiment of the present invention. can do. The flame retardant may be used alone or in combination of two or more.

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

(solvent)
In the curable composition according to the embodiment of the present invention, a solvent can be used for the purpose of reducing the viscosity of the curable composition, enhancing the thixo property, and improving the workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane and petroleum solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples thereof include ketone solvents; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

However, when the amount of the solvent blended is large, the toxicity to the human body may be high, and the volume shrinkage of the cured product may be observed. Therefore, the blending amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the components (A) and (B). Most preferably, it is substantially free.

(Other additives)
In the curable composition according to one embodiment of the present invention, other additives other than the above-mentioned additives are used, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product. May be good. Examples of such other additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, foaming agents, fungicides. Examples include ant agents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples of other additives include, for example, JP-A-4-69659, JP-A-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2001-72854. It is described in.

[3.2. Morphology of curable composition]
The curable composition according to one embodiment of the present invention can be prepared as a one-component curable composition in which all the compounding components are premixed, sealed and stored, and then cured by the humidity in the air after construction. Alternatively, the curable composition according to one embodiment of the present invention contains, as a curing agent, a curing catalyst, a filler, a plasticizer, water, etc., separately from the polymer composition containing the component (A) and the component (B). It is also possible to prepare a two-component curable composition in which the components are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferable.

When the curable composition is a one-component type, all the compounding components are pre-blended. Therefore, the moist-containing compounding components are dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding kneading. Is preferable. When the curable composition is a two-component type, it is not necessary to mix a curing catalyst with a main agent containing a polymer having a reactive silyl group, so that gelation occurs even if some water is contained in the compounding agent. Although there is little concern about this, dehydration and / or drying is preferable when long-term storage stability is required. As a method of dehydration and / or drying, heat drying method or vacuum dehydration method for solid matter such as powder, vacuum dehydration method or vacuum dehydration method for liquid matter, activated alumina, silica gel, quicklime, magnesium oxide, etc. The dehydration method used is suitable. In addition to such dehydration and / or drying methods, as dehydrating agents, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto An alkoxysilane compound such as propylmethyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration. Further, as a dehydrating agent, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water to dehydrate. Further, as a dehydrating agent, a small amount of an isocyanate compound may be blended and the isocyanate group may be reacted with water to dehydrate. Storage stability is improved by the addition of the alkoxysilane compound, the oxazolidine compound, and the isocyanate compound.

The amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). It is preferably in the range of 0.5 parts by weight to 10 parts by weight, and more preferably 1 part by weight to 5 parts by weight.

[3.3. Method for producing curable composition]
The method for producing the curable composition according to the embodiment of the present invention is not particularly limited, and for example, a method in which the above-mentioned components are blended and kneaded at room temperature or under heating using a mixer, a roll, a kneader or the like is suitable. Ordinary methods such as a method of dissolving and mixing the components using a small amount of a solvent can be adopted.

[3.4. Uses of curable composition]
When the curable composition according to one embodiment of the present invention is exposed to the atmosphere, it forms a three-dimensional network structure by the action of moisture and is cured into a solid having rubber-like elasticity. Therefore, one embodiment of the present invention also includes a cured product obtained by curing the curable composition.

The curable composition according to an embodiment of the present invention is a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, an adhesive, a molding agent, a vibration isolator, a vibration damping material, a soundproofing material, and foaming. It can be used for materials, paints, spray materials, etc. The cured product obtained by curing the curable composition according to one embodiment of the present invention is excellent in flexibility and adhesiveness, and therefore, among these, it is more preferable to use it as a sealing material or an adhesive.

In addition, electrical and electronic component materials such as solar cell backside encapsulants, electrical insulating materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact adhesives, spray sealants, crack repair materials, powder coatings. , Casting material, medical rubber material, medical adhesive, medical equipment sealing material, food packaging material, sealing material for joints of exterior materials such as siding boards, coating material, primer, conductive material for electromagnetic wave shielding, heat conduction Sexual materials, hot melt materials, electric and electronic potting agents, films, gaskets, various molding materials, wire-reinforced glass and laminated glass end faces (cut parts) rustproof / waterproof encapsulants, as well as automobile parts, electrical parts, It can be used for various purposes such as liquid sealants used in various machine parts. In addition, it can be used alone or with the help of primers as it can adhere to a wide range of substrates such as glass, porcelain, wood, metals, resin moldings, etc., and thus can also be used as various types of sealing and adhesive compositions. .. Further, the curable composition according to one embodiment of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, and an adhesive for floor finishing. Agents, wall finish adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, direct glazing sealants, double glazing sealants, SSG method sealants, or building working It can also be used as a sealing material for joints.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The number average molecular weight and the weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.
Liquid transfer system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Molecular weight: Polystyrene equivalent measurement temperature: 40 ° C
[Synthesis Examples 1 and 2] [Comparative Synthesis Example 1]
Isobutanol was added as an initial preparation solvent to the flask, heated to 105 ° C., subjected to nitrogen substitution, and then stirred, under a nitrogen atmosphere, the (meth) acrylic acid ester-based monomer and mercaptosilane shown in Table 1 were added. A mixed solution of 4 and 4-methoxyphenol and a solution of V-59 and isobutanol were added dropwise over 5 hours, and polymerization was carried out after 1 hour. A clear and viscous liquid was obtained by removing isobutanol under heating and reduced pressure from the isobutanol solution of the obtained (meth) acrylic acid ester-based copolymer. Based on the above, (meth) acrylic acid ester-based polymers having a reactive silyl group and having the molecular weights shown in Table 1 (polymers (A-1) to (A-2), comparative polymers (A-1)). Got

The abbreviations of the (meth) acrylic acid ester-based monomer and solvent in Table 1 and the details of the polymerization initiator are as follows.
MMA: Methyl methacrylate BA: Butyl acrylate SMA: Stearyl methacrylate γ-DSMA: 3- (Methyldimethoxysilyl) propyl γ-DSM: 3- (Methyldimethoxysilyl) propyl mercaptan α-MSMA: Dimethyl methacrylate Methoxysilyl) Methyl α-MSM: (Dimethylmethoxysilyl) Methyl mercaptan IBA: Isobutanol V-59: 2,2'-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
MQ: 4-methoxyphenol

[Synthesis Example 3]
Polyoxypropylene diol having a number average molecular weight of about 4,500 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocovalent glyme complex catalyst to obtain hydroxyl group-terminated polyoxypropylene having a number average molecular weight of about 15,000. It was. Subsequently, 1.2 equivalents of a methanol solution of sodium methoxydo was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene to distill off methanol at 140 ° C., and then 1.6 equivalents of 3-chloro-1-propene. Was added to convert the terminal hydroxyl group into an allyl group. Next, 36 ppm by weight of a platinum divinyl disiloxane complex (3 wt% isopropyl alcohol solution in terms of platinum) and 1.7 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and 90 parts by weight were added. By reacting at ° C. for 2 hours, polyoxypropylene (polymer (B-1)) having an average of 1.6 silyl groups per molecule and a methyldimethoxysilyl group at the end having a number average molecular weight of 15,000. Got

[Examples 1 to 4] [Comparative Examples 1 and 2]
(Meta) acrylic acid ester-based polymer having a reactive silyl group (polymers (A-1), (A-2), comparative polymer (polymers (A-1), (A-2)) obtained in Synthesis Examples 1 and 2 or Comparative Synthesis Example 1 A-1)), the polyoxypropylene (polymer (B-1)) obtained in Synthesis Example 3, and the components shown in Tables 2 and 3 were blended in the weight ratios shown in Tables 2 and 3. It was mixed by hand and defoamed with a centrifuge. Then, the obtained curable composition was made into a sheet-like test piece having a thickness of 3 mm and completely cured by putting it in a dryer at 23 ° C. and 50% RH for 3 days and further in a dryer at 50 ° C. for 4 days. ..

Details of the curing catalyst in Tables 2 and 3 are as follows.
Neostan U-220H: Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd.)
Neostan U-28: Tin octylate (manufactured by Nitto Kasei Co., Ltd.)

[Evaluation of tensile properties of cured products]
After punching the sheet-shaped specimens having a thickness of 3 mm obtained in Examples 1 to 4 and Comparative Examples 1 and 2 into a No. 3 dumbbell mold, tension was performed at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation. The test was performed and 100% modulus and elongation at break (denoted as M100 and EB, respectively) were measured. The results are shown in Tables 2 and 3.

From the results in Tables 2 and 3, it has an organic polymer having a reactive silyl group at the terminal of the molecular chain and a reactive silyl group having a monofunctional monoalkoxysilyl group at the α-position of the electron-withdrawing group at the terminal of the main chain ( In Examples 1 to 4 in which the curable composition containing the meta) acrylic acid ester polymer is cured, the same organic polymer and the reactive silyl having a bifunctional dialkoxysilyl group at the γ position of the electron-withdrawing group are used. It can be seen that the elongation of the obtained cured product is higher than that of Comparative Examples 1 and 2 in which the (meth) acrylic acid ester-based polymer having a group at the end of the main chain is cured.

That is, an organic polymer such as a polyoxyalkylene polymer having a reactive silyl group has a reactive silyl group having a monofunctional monoalkoxysilyl group at the α-position of the electron-withdrawing group at the terminal of the main chain (meth). It can be seen that the addition of the acrylate-based polymer imparts excellent weather resistance to the cured product and the cured product exhibits high elongation.

The present invention is used for sealing materials for buildings, ships, automobiles, roads, etc., adhesives, adhesives, molding agents, vibration-proofing materials, vibration-damping materials, soundproofing materials, foam materials, paints, spraying materials, etc. be able to.

Claims (6)

A (meth) acrylic acid ester-based polymer (A) having a reactive silyl group represented by the following general formula (1) at the end of the main chain:
-W-CH _2- SiR ¹ ₂ (OR ² ) ... (1)
In the general formula (1), W is -CO-O-, -CO-N (R ³ )-, -O-CO-N (R ³ )-, -N (R ³ ) -CO-O-,- A linking group selected from N (R ³ ) -CO-N (R ³ )-, -S-CO-NH-, -NH-CO-S-, and -S-, where R ³ is a hydrogen atom. Alkyl groups having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted, alkenyl having 1 to 18 carbon atoms in a cyclic, linear or branched chain which may be halogen substituted. It is a group or an aryl group having 6 to 18 carbon atoms, and R ¹ is an independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is an aralkyl group of 7 to 20, and R ² is an alkyl group. The (meth) acrylic acid ester-based polymer (A) according to claim 1, further having the reactive silyl group in the side chain. The (meth) acrylic acid ester-based polymer (A) according to claim 1 or 2,
An organic polymer (B) having a reactive silyl group at the end of the molecular chain other than the (meth) acrylic acid ester-based polymer (A) having a reactive silyl group represented by the general formula (1) at the end of the main chain. ) Containing a curable composition. The curable composition according to claim 3, wherein the reactive silyl group of the organic polymer (B) having a reactive silyl group at the end of the molecular chain is a methyldimethoxysilyl group. The curable composition according to claim 3 or 4, which contains a tin-based catalyst. A cured product obtained by curing the curable composition according to any one of claims 3 to 5.