JP2021155507A - POLYMER CONTAINING Si-F BOND AND CURABLE COMPOSITION CONTAINING THE SAME - Google Patents

Abstract

To provide a silicon group-containing polyoxyalkylene polymer containing an Si-F bond which is a moisture curable polymer exhibiting quick curability even when an organotin-based catalyst is not substantially used and to provide a moisture curable polymer comprising the same with good storage stability.SOLUTION: There is provide a silicon group-containing polyoxyalkylene based polymer containing an Si-F bond (A) in which the molar ratio of an Si-F bond to the total mol number of an Si-F bond and an Si-Z bond (Z is reactive group other than fluorine) in the whole polymer is 60 to 90%.SELECTED DRAWING: None

Description

The present invention relates to a silicon group-containing polymer containing a Si—F bond and a curable composition containing the polymer.

A polymer containing at least one reactive silicon group in the molecule is crosslinked by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like even at room temperature to obtain a rubber-like cured product. It is known to have the property of being

Among these polymers having a reactive silicon group, the organic polymer whose main chain skeleton is a polyoxyalkylene polymer has already been industrially produced and is widely used in sealing materials, adhesives, paints and the like. in use.

When these polymers are used as curable compositions used in sealants, adhesives, paints, etc., various properties such as curability, adhesiveness, and mechanical properties of the cured product are required.

On the other hand, a silicon group-containing polymer containing a Si—F bond and a curable composition containing the polymer are disclosed in Patent Document 1, and are excellent without using an organotin catalyst. It is known that it has curability and also exhibits excellent fast-curing property. Such curable compositions can be used in applications such as sealants, adhesives and paints.

International Publication No. 2008/032539

A polymer having a silicon group-containing polyoxyalkylene-based skeleton containing a Si—F bond synthesized by the method described in Document 1 tends to generate black foreign substances during production, which causes a problem that processing becomes difficult. In addition, there was room for improvement in that coloring and offensive odors tended to occur after storage. In the present invention, a wet-curable polymer which is a polymer having a property of being cured by moisture at room temperature and which exhibits fast curing even when an organic tin-based catalyst is not substantially used, and a wetness containing the same. It is an object of the present invention to provide a partially curable composition with good storage stability.

In view of the above circumstances, as a result of diligent studies by the present inventors, Si—F bond with respect to the total number of moles of Si—F bond and Si—Z bond (Z is a reactive group other than fluorine) in the total polymer. We have found that the above problem can be solved by controlling the molar ratio of the above, and have completed the present invention.

That is, the present invention
(1) A silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, which is a Si—F bond and a Si—Z bond (Z is a reactive group other than fluorine) in the total polymer. The present invention relates to a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, wherein the molar ratio of the Si—F bond to the total number of moles of (is) is 60 to 90%.
(2) The Si—F bond according to (1) above, wherein the molar ratio of the Si—F bond to the total number of moles of the Si—F bond and the Si—Z bond in the total polymer is 70 to 85%. The present invention relates to a silicon group-containing polyoxyalkylene polymer (A) containing.
Further, (3) the silicon group containing the Si—F bond is represented by the following general formula (1):
−SiF _a R ¹ _b Z _c (1)
(In the formula, R ¹ is an independently substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO− (R ² is independently substituted or substituted with 1 to 20 carbon atoms, respectively). Indicates any of the organosiloxy groups represented by) (is an unsubstituted hydrocarbon group). Z is an independently reactive group other than fluorine. A is any of 1, 2 and 3. b is either 0, 1, 2, c is any of 0, 1, 2, a + b + c If a 3 .b or c is 2, two ^{R 1} or two Z is It relates to the silicon group-containing polyoxyalkylene polymer (A) containing the Si—F bond according to the above (1) or (2), which may be the same or different from each other.
(4) The present invention relates to a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond according to any one of (1) to (3) above, which has a number average molecular weight of 3000 to 30000.
(5) A silicon group-containing polyoxyalkylene polymer containing a Si—F bond according to any one of (1) to (4) above, wherein Z in the general formula (1) is an alkoxy group. Regarding A).
(6) The silicon group-containing polyoxyalkylene polymer (A) containing the Si—F bond according to any one of (1) to (5) above, and the reactive silicon group having no Si—F bond. A curable composition containing the polymer (B), wherein the polymer (A) is 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymer (B). ..
(7) The curable composition according to (6) above, which further contains a curing catalyst (C).
(8) The curable composition according to (7) above, wherein the curing catalyst (C) is an amine compound.
(9) The present invention relates to a sealing material using the curable composition according to any one of (6) to (8) above.
(10) The present invention relates to an adhesive made by using the curable composition according to any one of (6) to (8) above.
(11) The present invention relates to a cured product obtained by curing the curable composition according to any one of (6) to (8) above.
Further, (12) a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, wherein the reactive group of the reactive silicon group-containing polyoxyalkylene polymer is fluorinated by a fluorinating agent. Converted to fluorine atoms, the molar ratio of Si—F bonds to the total number of moles of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer is 60 to 90%. The present invention relates to a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, which is converted so as to be.

The polymer and curable composition of the present invention have excellent curability even when an organic tin-based catalyst is not used, and further have excellent storage stability. Such curing of the present invention can be suitably used for a sealing material and an adhesive.

Hereinafter, the present invention will be described in detail. The "reactive silicon group" in the present specification is a silicon-containing group that has a hydrolyzable group or a hydroxyl group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. A "reactive group" is a hydrolyzable group or a hydroxyl group.

The curable composition containing the silicon group-containing polyoxyalkylene polymer (A) (also referred to as the polymer (A)) containing the Si—F bond of the present invention and the polymer (A) is moist even at room temperature. It shows curability by the minute.

A silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond of the present invention, and a polymer (B) having a reactive silicon group having no Si—F bond (also referred to as a polymer (B)). ), The curable composition in combination is characterized by exhibiting rapid curability as compared with the case where only the polymer (B) containing a reactive silicon group having no Si—F bond is used.

<Silicon group-containing polyoxyalkylene polymer (A) containing Si—F bond>
Hereinafter, the silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond in the present invention will be described.

(Silicon group containing Si—F bond)
The Si-F bond of the polymer (A) was effective even in any of the sites within the polymer molecule, as long as the terminal of the main chain or side chain -SiR _{'2 F,} in the main chain of the polymer If incorporated, it is represented in the form of -SiR'F- or ≡SiF (R'is independently F or any group).

The silicon group having a Si—F bond at the end of the main chain or the side chain includes the following general formula (1):
−SiF _a R ¹ _b Z _c (1)
(In the formula, R ¹ is an independently substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO− (R ² is independently substituted or substituted with 1 to 20 carbon atoms, respectively). Indicates any of the organosiloxy groups represented by) (is an unsubstituted hydrocarbon group). Z is an independently reactive group other than fluorine. A is any of 1, 2 and 3. b is either 0, 1, 2, c is any of 0, 1, 2, a + b + c If a 3 .b or c is 2, two ^{R 1} or two Z is The silicon group represented by () may be the same or different from each other.

Examples of the reactive group other than fluorine represented by Z in the general formula (1) include a hydroxyl group, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, and an aminooxy. Groups, mercapto groups, alkenyloxy groups and the like can be mentioned. Among these, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, a hydroxyl group and an alkoxy group are more preferable, and the hydrolysis property is mild and handled. An alkoxy group is particularly preferable from the viewpoint of ease of use.

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ² is a methyl group. Examples thereof include a triorganosyloxy group represented by ^{R 2} ₃ SiO − which is a phenyl group or the like. Of these, the methyl group is particularly preferred.

Specific examples of the silicon group represented by the general formula (1) include a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, and a fluorodiphenylsilyl group as silicon groups having no reactive group other than fluorine. Fluorine and other reactive groups such as groups, fluorodibenzylsilyl groups, difluoromethylsilyl groups, difluoroethylsilyl groups, difluorophenylsilyl groups, difluorobenzylsilyl groups, trifluorosilyl groups, difluoro (methoxymethyl) silyl groups, etc. As silicon groups having both, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodipropoxysilyl group, fluorodiphenoxy Examples thereof include a silyl group, a fluorobis (2-propenoxy) silyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, a difluorophenoxysilyl group, a fluorodichlorosilyl group, a difluorochlorosilyl group, and a fluoromethoxy (methoxymethyl) silyl group. .. Fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group are more suitable for ease of synthesis. Preferably, a fluorodimethylsilyl group, a fluoromethoxymethylsilyl group, a fluorodimethoxysilyl group and a fluorodiethoxysilyl group are particularly preferable, and a fluoromethoxymethylsilyl group is most preferable.

In silicon group having SiF bond, examples of those incorporated in the main chain of the _{polymer, -Si (CH 3) F -} , - Si (C 6 H 5) F -, - SiF 2 -, ≡ SiF and the like.

The polymer (A) of the present invention may contain two or more silicon groups having a Si—F bond. In that case, each silicon group may be the same or different.

The number of reactive silicon groups contained in one molecule of the polymer (A) of the present invention is preferably 0.5 to 6.0 on average, preferably 0.7 to 5.0. It is more preferable that there are 1.0 to 4.0 pieces. Further, a polymer (A) having an average number of reactive silicon groups of more than one per terminal can be used.

When the polymer (A) of the present invention is used, that is, even if the polymer (A) containing various Si—F groups as described above is used alone in the curable composition of the present invention. Alternatively, two or more kinds may be used in combination.

(Main clavicle)
The polyoxyalkylene polymer, which is the main chain skeleton of the polymer (A), has a general formula (2):
-R ³ -O- (2)
(In the formula, R ³ is a linear or branched alkylene group having 1 to 14 carbon atoms.) It is a polymer having a repeating unit represented by the formula, and R ³ in the general formula (2) is a carbon atom number. 1 to 14 and even 2 to 4 linear or branched alkylene groups are preferred. As a specific example of the repeating unit represented by the general formula (2),

And so on. The main clavicle of the polymer (A) may consist of only one type of repeating unit or may consist of two or more types of repeating units. In particular, when the polymer (A) is used as a sealant or the like, it is preferable that the polymer composed of a polyoxypropylene-based polymer as a main component is amorphous and has a relatively low viscosity.

(Method for producing polymer (A))
The method for producing the silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond is such that the silicon group of the reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine is Si—F. It is preferably carried out by a method of converting to a silicon group containing a bond.

As a method for producing a reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine, (i) a composite metal cyanide complex catalyst is used, and an epoxy compound is polymerized with an initiator having a hydroxyl group. A method of obtaining a hydroxyl group-terminated polyoxyalkylene polymer, converting the hydroxyl group of the obtained hydroxyl group-terminated polyoxyalkylene polymer into a carbon-carbon unsaturated group, and then adding a silane compound by a hydrosilylation reaction. (Ii) A hydroxyl group-terminated polyoxyalkylene polymer is obtained by a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst, and then the obtained hydroxyl group-terminated polyoxyalkylene polymer is obtained. , A method of reacting a compound having both a group that reacts with a hydroxyl group and a reactive silicon group, (iii) reacting a hydroxyl group-terminated polyoxyalkylene polymer with an excess polyisocyanate compound to have an isocyanate group at the terminal. After forming the polymer, a method of reacting a compound having both a group that reacts with an isocyanate group and a reactive silicon group is preferable.

Examples of the hydroxyl group-containing initiator used in the methods (i) and (ii) include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, methanol, ethanol, and the like. Examples thereof include those having one or more hydroxyl groups such as propanol, butanol, pentanol, hexanol, polyoxypropylene monoallyl ether, and polyoxypropylene monoalkyl ether.

Examples of the epoxy compound used in the methods (i) and (ii) include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.

Examples of the carbon-carbon unsaturated group used in the method (i) include a vinyl group, an allyl group, a metallicyl group, a propargyl group and the like. Of these, an allyl group is preferable.

As a method for converting the hydroxyl group of (i) into a carbon-carbon unsaturated group, an alkali metal salt is allowed to act on the hydroxyl group terminal-containing polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of causing.

Examples of the halogenated hydrocarbon compound used in the method (i) include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, vinyl iodide, and allyl iodide. , Allyl iodide, Propargyl iodide, etc.

Examples of the hydrosilane compound used in the method (i) include trimethoxysilane, triethoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, dimethoxymethylsilane, (chloromethyl) dimethoxysilane, and (methoxymethyl) dimethoxysilane. , (N, N-diethylaminomethyl) dimethoxysilane, and the like can be used.

The hydrosilylation reaction used in method (i) is accelerated by various catalysts. As the hydrosilylation catalyst, a known catalyst may be used. For example, a carrier in which platinum is supported on a carrier such as alumina, silica, or carbon black, platinum chloride acid; a platinum chloride acid complex composed of platinum chloride acid and alcohol, aldehyde, ketone, or the like; a platinum-olefin complex [for example, Pt (CH). ₂ = CH ₂ ) ₂ (PPh ₃ ), Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ]; Platinum-vinylsiloxane complex [Pt {(vinyl) Me ₂ SiOSiMe ₂ (vinyl)}, Pt {Me (vinyl) SiO} ₄ ]; Platinum-phosphine complex [Ph (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ]; Platinum-phosphite complex [Pt {P (OPh) ₃ } ₄ ] and the like can be used.

Examples of the compound having both a hydroxyl group-reacting group and a reactive silicon group that can be used in the method (ii) include 3-isocyanappropyltrimethoxysilane, 3-isocyanuppropyldimethoxymethylsilane, and 3-isocyanuppropyltriethoxysilane. , Isocyanates such as isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; mercapto such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane. Silanes; Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropyltriethoxysilane can be used.

Examples of the polyisocyanate compound that can be used in the method (iii) include aromatic polyisocyanates such as toluene (trilen) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. Can be mentioned.

Examples of the compound having both a group that reacts with an isocyanate group and a reactive silicon group that can be used in the method (iii) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, and γ-aminopropyltriethoxysilane. , N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxymethylsilane, N- (β-aminoethyl) -γ-aminopropyltriethoxy Silane, γ- (N-phenyl) aminopropyltrimethoxysilane, γ- (N-phenyl) aminopropyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylamino Amino group-containing silanes such as methyltrimethoxysilane and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; Examples thereof include mercapto group-containing silanes such as methoxysilane and γ-mercaptopropyldimethoxymethylsilane; and the like.

Various fluorinating agents can be used as a method for converting the silicon group of the obtained reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine into a silicon group containing a Si—F bond. preferable.

Specific examples of the fluorinating agent include NH ₄ F, HF, BF _3, etc., but from the viewpoint of simplicity, efficiency, safety, etc. of the reaction, fluorination of the alkoxysilyl group using _{BF 3 is preferable.} .. As BF ₃ , BF ₃ gas, BF ₃ ether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex and the like can be used, but fluorination of the alkoxysilyl group using the _{BF 3 methanol complex can be used.} It is preferable because no salt or the like is generated in the by-product and post-treatment is easy. Further, there is no need of heating or the like in the reaction, it is preferable to use a BF ₃ methanol complex from the fact that progresses also readily fluorinated at room temperature, as a coordination number of 2 represented by the chemical formula BF ₃ · 2 MeOH Is more preferred.

The polymer (A) in the present invention is the molar ratio of Si—F bonds (fluorine) to the total number of moles of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer. It is characterized in that the conversion rate) is 60 to 90%. Here, 60 to 90% means 60% or more and 90% or less.

When the molar ratio of Si—F bonds to the total number of molars of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer (A) is 60% or more, the polymer. By cross-linking the reactive groups on the silicon groups remaining in (A), it is possible to solve the problem that the viscosity increases and it becomes difficult to use.

When the molar ratio of Si—F bonds to the total number of moles of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer (A) is 90% or less, the polymer. It is possible to solve the problems that yellow coloring occurs during storage of (A) and loses transparency, and that an offensive odor is generated. That is, when trying to exceed 90% and approach 100%, an excess amount of fluorinating agent is usually required in the manufacturing process. Therefore, the component derived from the fluorinating agent, which is a raw material, tends to remain in the polymer (A), and as a result, yellow coloring occurs during storage of the polymer (A), which causes loss of transparency and an offensive odor. However, by setting the molar ratio to 60 to 90%, it was possible to achieve both the problems of storage stability such as suppression of viscosity increase and generation of coloring and offensive odor during storage.

The reaction temperature for fluorination is preferably less than 80 ° C., more preferably less than 50 ° C., and even more preferably less than 40 ° C. because the fluorinating agent is unstable at high temperatures. The lower limit of the reaction temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and even more preferably 20 ° C. or higher.

The reaction time for fluorination is preferably 5 minutes to 10 hours, more preferably 1 hour to 6 hours.

In the present invention, by reducing the amount of the fluorinating agent, the silicon groups of the reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine are partially fluorinated. In order to solve the above problems, the molar ratio of Si—F bonds to the total number of moles of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer is 60 to 60 to Adjust the amount of fluorinating agent to 90%. This makes it possible to suppress the yellow coloring, offensive odor, and increase in viscosity that occur when the polymer (A) is stored alone. Further, the molar ratio of Si—F bond is preferably 70 to 85%.
That is, the present invention is a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, in which the reactive group of the reactive silicon group-containing polyoxyalkylene polymer is fluorinated. Converted to fluorine atoms by the agent, the molar ratio of Si—F bonds to the total number of moles of Si—F bonds and Si—Z bonds (Z is a reactive group other than fluorine) in the total polymer is 60 to 90. Included is a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, which is converted to%. Further, the molar ratio of Si—F bond is preferably 70 to 85%.

When a polyoxyalkylene polymer containing a dimethoxymethylsilyl group is used as the raw material polymer and the silicon group in the raw material polymer is converted into a silicon group containing a Si−F bond, the fluorination rate is ¹ H−. It can be determined accurately by NMR. Specifically, when the methoxy group on silicon is converted to a fluoro group, the peak of the methyl group on silicon shifts, so that the difluoromethylsilyl group and the monofluoromethoxymethylsilyl group in the polymer (A), The molar ratio of the dimethoxymethylsilyl group can be obtained and the fluorination rate can be calculated.

In addition, in the present invention, the molar ratio of Si—F bond to the total number of molars of Si—F bond and Si—Z bond (Z is a reactive group other than fluorine) in the total polymer is 60 to 90%. "In all polymers" in "Aru" refers to the entire polymer obtained by partially fluorinating the raw material polymer with a fluorinating agent, and the weight in which the raw material polymer is completely fluorinated is included. It may contain a polymer that has not been coalesced or fluorinated, and means the fluorination rate of the polymer as a whole.

After the reaction, it is preferable to remove the components derived from the fluorinating agent by vacuum volatilization or the like, and the low molecular weight components of boron and fluorine, which are the residues of the reaction, are completely removed from the produced polymer (A). Is even more preferable.

The obtained silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond may have a linear or branched structure, and its number average molecular weight is 3,000 to 3,000 in terms of polystyrene in GPC. 30,000 is preferable. If the number average molecular weight is less than 3,000, it tends to be inconvenient in terms of elongation characteristics of the cured product, and if it exceeds 30,000, it tends to be inconvenient in terms of workability due to high viscosity.

The molecular weight distribution of the silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond is preferably 1.6 or less, more preferably 1.4 or less, still more preferably 1.3 or less. Further, from the viewpoint of improving various mechanical characteristics such as improving the durability and elongation of the cured product, 1.2 or less is preferable. The molecular weight distribution can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC.

<Curable composition>
In the present invention, the silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond is mixed with a reactive silicon group-containing polymer (B) having no Si—F bond to achieve rapid curing. A curable composition having can be obtained.

<Reactive silicon group-containing polymer (B) without Si—F bond>
The reactive silicon group-containing polymer (B) having no Si—F bond may have a linear or branched structure, and its number average molecular weight is about 3,000 to 100,000 in terms of polystyrene in GPC. It is preferably more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 3,000, it tends to be inconvenient in terms of elongation characteristics of the cured product, and if it exceeds 100,000, it tends to be inconvenient in terms of workability due to high viscosity.

The molecular weight distribution of the reactive silicon group-containing polymer (B) having no Si—F bond is preferably 1.6 or less, more preferably 1.4 or less, still more preferably 1.3 or less. Further, from the viewpoint of improving various mechanical characteristics such as improving the durability and elongation of the cured product, 1.2 or less is preferable. The molecular weight distribution can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC.

(Reactive silicon group without Si—F bond)
As the reactive silicon group having no Si—F bond contained in the polymer (B), the general formula (3):
−SiR ⁴ _3-d Y _d (3)
(In the formula, R ⁴ is an independently substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁵ ₃ SiO− (R ⁵ is an independent hydrocarbon having 1 to 20 carbon atoms, respectively). It indicates any of the organosiloxy groups represented by) (which is a group). Y is an independently reactive group other than fluorine. D is any of 1, 2, and 3). It is preferably a silicon group to be used.

The reactive group of the polymer (B) that does not have a Si—F bond is not particularly limited, and any conventionally known reactive group may be used. Specific examples thereof include a hydroxyl group, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is selected from the viewpoint of mild hydrolyzability and easy handling. Especially preferable.

If two or more reactive groups are attached to the reactive silicon group, they may be the same or different.

Specific examples of R ⁴ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ⁵ is a methyl group. triorganosiloxy group represented by R ⁵ ₃ SiO- a phenyl group, and the like. Of these, the methyl group is particularly preferred.

More specific examples of the reactive silicon group of the polymer (B) that does not have a Si—F bond include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethyl group. Examples thereof include a silyl group, a diisopropoxymethylsilyl group, a methoxydimethylsilyl group, an ethoxydimethylsilyl group, a (methoxymethyl) dimethoxysilyl group, and a (chloromethyl) dimethoxysilyl group. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group and a (methoxymethyl) dimethoxysilyl group are particularly preferable, because they have high activity and good curability can be obtained. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. The triethoxysilyl group is particularly preferable because the alcohol produced by the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

Further, a polymer having a reactive silicon group having three reactive groups on a silicon atom gives a curable composition having high curability and good restorability, durability and creep resistance. Tendency and preferred.

The number of reactive silicon groups contained in one molecule of the polymer (B) of the present invention is preferably 0.5 to 6.0 on average, preferably 0.7 to 5.0. It is more preferable that there are 1.0 to 4.0 pieces. Further, a polymer (B) having an average number of reactive silicon groups of more than one per terminal can be used.

(Main clavicle)
The main chain skeleton of the polymer (B) of the present invention is not particularly limited, and those having various main chain skeletons can be used, but those that are compatible with the polymer (A) are preferable.

Specific examples of the main chain skeleton of the polymer (B) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxy. Polyoxyalkylene-based polymers such as butylene copolymers; ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and / or styrene, etc. Copolymer with, polybutadiene, isoprene, copolymer of butadiene with acrylonitrile, styrene, etc., hydrocarbon polymer such as hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; Adipine A polyester polymer obtained by condensing a dibasic acid such as an acid with glycol or ring-opening polymerization of lactones; obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate ( Meta) Acrylic acid ester-based polymer; Vinyl-based polymer obtained by radical polymerization of (meth) acrylic acid ester-based monomer, vinyl acetate, acrylonitrile, styrene and other monomers; Graft polymer obtained by 10. Polypolymers such as polyamide 11 by condensate of ε-aminoundecanoic acid, polyamide 12 by ring-open polymerization of ε-aminolaurolactum, and copolymerized polyamide having two or more components among the above-mentioned polyamides; Examples thereof include organic polymers such as polycarbonate-based polymers and diallylphthalate-based polymers produced by shrink-polymerizing bisphenol A and carbonyl chloride. Further, a polysiloxane-based polymer such as polydiorganosiloxane can also be used. Among these, saturated hydrocarbon-based polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene-based polymers, (meth) acrylic acid ester-based polymers, and polysiloxane-based polymers are The cured product obtained when used as a curable composition has a relatively low glass transition temperature, and is more preferable because it has excellent cold resistance. Polyoxyalkylene-based polymers and (meth) acrylic acid ester-based polymers are even more preferable. , Polyoxyalkylene-based polymers are most preferable.

(Polyoxyalkylene polymer)
When a polyoxyalkylene polymer is used as the main chain of the polymer (B), the main chain is -R ^6- O- (in the formula, R ⁶ is a linear or branched alkylene having 1 to 14 carbon atoms. It has a repeating unit represented by), and R ⁶ is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

As a method for producing a reactive silicon group-containing polyoxyalkylene polymer used as the polymer (B) without a Si—F bond, (i) a composite metal cyanide complex catalyst is used as an initiator having a hydroxyl group. After obtaining a hydroxyl group-terminated polyoxyalkylene polymer by a method of polymerizing an epoxy compound, the hydroxyl group of the obtained hydroxyl group-terminated polyoxyalkylene polymer is converted into a carbon-carbon unsaturated group to hydrosilylate the silane compound. Method of adding by reaction, (iii) Method of reacting a hydroxyl group-terminated polyoxyalkylene polymer with a compound having both a group that reacts with a hydroxyl group and a reactive silicon group, (iii) a hydroxyl group-terminated polyoxyalkylene polymer. Examples thereof include a method in which the coalescence is reacted with an excess polyisocyanate compound to form a polymer having an isocyanate group at the terminal, and then a compound having both a group that reacts with the isocyanate group and a reactive silicon group is reacted.

(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, or the like. 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 above olefin compound is copolymerized. After that, it can be obtained by a method such as hydrogenation, but in the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer, it is easy to introduce a functional group at the terminal, the molecular weight can be easily controlled, and the terminal functional group can be easily obtained. It is preferable because the number can be increased, and an isobutylene-based polymer is particularly preferable.

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

In the isobutylene-based polymer, all the monomer units may be formed from isobutylene units, or copolymers with other monomers may be used, but from the viewpoint of rubber properties, 50 repeating units derived from isobutylene are used. It is preferably contained in an amount of 80% by weight or more, more preferably 80% by weight or more, and particularly preferably 90 to 99% by weight.

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, inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, Vol. 15, 2843. 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.

Examples of the method for producing a reactive silicon group-containing saturated hydrocarbon polymer having no Si—F bond, which is used as the polymer (B), include Tokusho 4-69659, Tokuhei 7-108928, and Japanese Patent Application Laid-Open No. Although it is described in each specification of Japanese Patent Application Laid-Open No. 63-254149, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Application Laid-Open No. 1-197509, Japanese Patent Application Laid-Open No. 2539445, Japanese Patent Application Laid-Open No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882. , Not particularly limited to these.

((Meta) acrylic acid ester polymer)
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, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Truyl acid, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Stearyl (meth) acrylic acid, glycidyl (meth) acrylic acid, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, ( Perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethylmethyl) (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) ) Examples thereof include (meth) acrylic acid-based monomers such as 2-perfluorohexyl ethyl acrylate, 2-perfluorodecyl ethyl (meth) acrylate, and 2-perfluorohexadecyl ethyl (meth) acrylate.

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 vinyl-based monomers 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; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid monoalkyl and dialkyl esters; fumaric acid, fumaric acid monoalkyl and dialkyl esters; maleimide, methyl Maleimide-based monomers such as maleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; acrylamide, Amido group-containing vinyl-based monomers such as methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnate; alkens such as ethylene and propylene; conjugated diene such as butadiene and isoprene Kind: Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

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

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, it is a (meth) acrylic acid ester-based polymer having a molecular weight distribution of 1.6 or less, preferably 1.4 or less, and having a high proportion of crosslinkable functional groups at the end of the molecular chain (meth). In order to obtain an acrylic acid ester polymer, it is preferable to use a living radical polymerization method.

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 Mattyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc), 1995, Vol. 117, p. 5614.

As a method for producing a reactive silicon group-containing (meth) acrylic acid ester-based polymer having no Si—F bond, which is used as the polymer (B), for example, Japanese Patent Publication No. 3-14608, Japanese Patent Publication No. 4-55444 A production method using a free radical polymerization method using a chain transfer agent is disclosed in Japanese Patent Application Laid-Open No. 6-21922. Further, Japanese Patent Application Laid-Open No. 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.

(Polymer (B) consisting of two or more types of main clavicle)
The polymer (B) composed of these various main chain skeletons may be used alone or in combination of two or more. Specifically, a polyoxyalkylene polymer having a reactive silicon group having no Si—F bond, a saturated hydrocarbon polymer having a reactive silicon group having no Si—F bond, and a Si—F bond A polymer obtained by blending two or more kinds selected from the group consisting of (meth) acrylic acid ester-based polymers having a reactive silicon group that does not have can also be used.

A weight obtained by blending a polyoxyalkylene polymer containing a reactive silicon group having no Si—F bond and a (meth) acrylic acid ester polymer containing a reactive silicon group having no Si—F bond. The method for producing the coalescence has been proposed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc., but is particularly limited thereto. It's not a thing. A preferred specific example is the following general formula (4): which has a reactive silicon group and has a substantially molecular chain.
-CH ₂ -C (R ⁷ ) (COOR ⁸ )-(4)
(In the formula, R ⁷ indicates a hydrogen atom or a methyl group, R ⁸ indicates an alkyl group having 1 to 8 carbon atoms), and a (meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms. Quantitative unit and the following general formula (5):
-CH ₂ -C (R ⁷ ) (COOR ⁹ )-(5)
(In the formula, R ⁷ is the same as above, and R ⁹ indicates an alkyl group having 10 or more carbon atoms) from a (meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms. This is a method for producing a polyoxyalkylene-based polymer having a reactive silicon group having no Si—F bond by blending the copolymer.

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

^{The R 9} of the general formula (5) includes, for example, a long chain having 10 or more carbon atoms such as a lauryl group, a tridecylic group, a cetyl group, a stearyl group, and a behenyl group, usually 10 to 30, preferably 10 to 20. Alkyl groups can be mentioned. 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 copolymer is substantially composed of the monomer units of the formulas (4) and (5), and the term "substantially" as used herein means the copolymer. It means that the total of the monomer units of the formulas (4) and (5) existing therein exceeds 50% by weight. The total of the monomer units of the formulas (4) and (5) is preferably 70% by weight or more.

The abundance ratio of the monomer unit of the formula (4) to the monomer unit of the formula (5) is 95: 5 to 4 by weight.
0:60 is preferable, and 90:10 to 60:40 is more preferable.

Examples of the monomer unit other than the formulas (4) and (5) that may be contained in the copolymer include acrylic acids such as acrylic acid and methacrylic acid; N-methylol acrylamide and N-methylol methacrylic amide. Amide groups such as amide groups, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and monomers containing nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate; other acrylonitrile, styrene, α-methylstyrene, alkylvinyl ether, vinyl chloride, etc. Monomer units derived from vinyl acetate, vinyl propionate, ethylene and the like can be mentioned.

It is made by blending a saturated hydrocarbon-based polymer containing a reactive silicon group without a Si-F bond and a (meth) acrylic acid ester-based copolymer containing a reactive silicon group without a Si-F bond. The polymer has been proposed in JP-A-1-168764, JP-A-2000-186176, etc., but is not particularly limited thereto.

Further, as a method for producing a polymer obtained by blending a (meth) acrylic acid ester-based copolymer containing a reactive silicon group having no Si—F bond, there is no other Si—F bond. A method of polymerizing a (meth) acrylic acid ester-based monomer in the presence of a polymer containing a reactive silicon group 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.

(Amount ratio of polymer (A) to polymer (B))
By mixing the polymer (A) with the polymer (B), a fast-curing composition can be obtained. The fast-curing property is determined by the ratio of Si—F bonds present in the polymer (A) to all the reactive groups on the silicon groups present in the polymer (A) and the polymer (B). .. The mixing ratio of the polymer (A) and the polymer (B) is preferably 0.01 to 50 parts by weight of the polymer (A) with respect to 100 parts by weight of the polymer (B). It is more preferably a part. If the polymer (A) is smaller than 0.01 parts by weight, the effect of accelerating the curing rate may not be sufficient, and if the polymer (A) is larger than 50 parts by weight, the strength of the cured product becomes extremely strong. It may decrease or the curing may not proceed sufficiently.

<Curing catalyst (C)>
The curable composition of the present invention contains a polymer (A) or a polymer (A) and a polymer (B), and may further contain a curing catalyst (C).

The curing catalyst (C) used in the present invention has a role of promoting a reaction of hydrolyzing and condensing the reactive silicon groups of the polymer (A) or the polymer (B) to crosslink them.

As the curing catalyst (C), various already known types such as an organic tin compound, a carboxylic acid metal salt, an amine compound, a carboxylic acid, an alkoxy metal, and an inorganic acid can be used. However, from an environmental point of view, it is preferable to use a non-organic tin-based compound as the curing catalyst. In particular, it is preferable to use an amine compound as a curing catalyst because the curable composition of the present invention can be rapidly cured even though it is a non-organic tin catalyst.

The amine compound that can be used as the curing catalyst (C) of the present invention also includes a nitrogen-containing cyclic compound such as pyridine. Specific examples of amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine and stearylamine. , Cyclone primary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, Adipose secondary amines such as disetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine; triallylamine , Oleylamine, and other aliphatic unsaturated amines; aromatic amines such as aniline, laurylaniline, stearylaniline, triphenylamine; pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylamino) Pyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2-piperidin methanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl- 1,4,5,6-Tetrahydropyrimidine, 1,8-diazabicyclo (5,4,5) undecene-7 (DBU), 6- (dibutylamino) -1,8-diazabicyclo (5,4,5) undecene Heterocyclic formulas such as -7 (DBA-DBU), 1,5-diazabicyclo (4,3,0) nonen-5 (DBN), 1,4-diazabicyclo (2,2,2) octane (DABCO), aziridine, etc. Compounds and other amines include monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N'. -Dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminop Amines such as ropyramine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylene diamine, 2,4,6-tris (dimethylaminomethyl) phenol Classes; guanidines such as guanidine and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide, and the like, but are not limited thereto.

Among them, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, DBN; guanidines such as guanidine and diphenylguanidine; butyl biguanide, 1-o-tolylbiguanide and the like. Biguanides such as 1-phenylbiguanide are preferable because they show high activity. Aryl-substituted biguanides such as 1-o-tolylbiguanide and 1-phenylbiguanide are preferable because they exhibit high adhesiveness.

Further, although the amine compound is basic, the amine compound having a pKa value of the conjugate acid of 11 or more is preferable because of its high catalytic activity. In particular, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are preferable because the pKa value of the conjugate acid is 12 or more and exhibits high catalytic activity.

From the viewpoint of ease of handling and safety, it is preferable to use an alkylamine having 5 to 20 carbon atoms, and more preferably an alkylamine having 6 to 15 carbon atoms. When the number of carbon atoms is smaller than this range, it tends to volatilize and the odor tends to increase. When the number of carbon atoms is larger than this range, it tends to become solid at room temperature, and compatibility with the polymer (A) may become difficult. From the viewpoint of availability, octylamine, 2-ethylhexylamine, laurylamine, and 3-diethylaminopropylamine are more preferable.

In the present invention, an amino group-containing silane coupling agent (hereinafter referred to as aminosilane) can also be used as the amine compound of the curing catalyst (C). Aminosilane is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and a substituted or unsubstituted amino group. Examples of the substituent of the substituted amino group include an alkyl group, an aralkyl group and an aryl group. Examples of the hydrolyzable silicon group include those in which Y is a hydrolyzable group among the groups represented by the general formula (3). Specific examples of the hydrolyzable group include groups already exemplified, but methoxy group, 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. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-( 2-Aminoethyl) Aminopropyltrimethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyldimethoxysilane, γ- (2-Aminoethyl) Aminopropyltriethoxysilane, γ- (2-Aminoethyl) Aminopropylmethyl Diethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltri Methoxysilane, 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-phenylaminomethyltrimethoxysilane , (2-Aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like.

As the aminosilane of the curing catalyst (C), an aminosilane _{having an amino group (-NH 2} ) is preferable from the viewpoint of curability, and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ from the viewpoint of availability. -Aminopropylmethyldimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferred.

Further, a ketimine compound that produces the above amine compound by hydrolysis can also be used as the curing catalyst (C) of the present invention.

Specific examples of the curing catalyst (C) other than the amine compound include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, and the like. 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, etc. Carboxylic acid; Derivatives of the above-mentioned carboxylic acid (carboxylic acid anhydride, ester, amide, nitrile, acyl chloride); tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, carboxylic acid Carboxylic acid metal salts such as titanium acid, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium Titanium compounds such as tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetatete); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, 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 (Tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate, dioctyltin bis (ethylmaleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxyside) ), Dibutenyl tin oxide, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction of dibutyltin oxide and phthalic acid ester. Organic tin compounds such as substances; aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetacetate), diisopropoxyaluminum ethylacetacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate) Kind: Various metal alkoxides such as tetrabutoxyhafnium; Organic acidic phosphoric acid esters; Organic sulfonic acids such as trifluoromethanesulfonic acid; Inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid. However, for the reasons mentioned above, the amount of the organic tin compound used is preferably 5 parts by weight or less, preferably 0.5 parts by weight or less, based on 100 parts by weight of the total amount of the polymer (A) and the polymer (B). Is more preferable, 0.05 parts by weight or less is further preferable, and it is particularly preferable that the content is not contained.

In the curable composition of the present invention, two or more kinds of curing catalysts (C) may be used in combination.

The amount of the curing catalyst (C) used is preferably about 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the polymer (A) and the polymer (B). About a portion is preferable. If the blending amount of the curing catalyst (C) is less than this range, it may be difficult to obtain a sufficient curing rate, and the catalytic activity may decrease after storage. On the other hand, if the blending amount of the curing catalyst (C) exceeds this range, the pot life may become too short and the workability may deteriorate.

<Additives>
In addition to the polymer (A), the polymer (B), and the curing catalyst (C), the curable composition of the present invention includes, as additives, an adhesiveness-imparting agent, a filler, a plasticizer, an adhesiveness-imparting resin, and the like. Solvents, diluents, property modifiers, tixogenic agents, epoxy group-containing compounds, photocurable substances, oxygen curable substances, antioxidants, light stabilizers, UV absorbers, epoxy resins, flame retardants, etc. Additives, may be added.

(Adhesive imparting agent)
A silane coupling agent can be used as an adhesive-imparting agent in the curable composition of the present invention. The silane coupling agent referred to here is a compound having a hydrolyzable silicon group and other functional groups in the molecule, and various adherends, that is, inorganic substances such as glass, aluminum, stainless steel, zinc, copper and mortar. When used as a base material or an organic base material such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, or 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. In addition, it is a compound that can function as a physical property adjusting agent, a dispersibility improving agent for an inorganic filler, and the like.

Examples of the hydrolyzable silicon group of the silane coupling agent include those in which Y is a hydrolyzable group among the groups represented by the general formula (2). Specific examples of the hydrolyzable group include groups already exemplified, but methoxy group, 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.

Examples of the functional group other than the hydrolyzable silicon group include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens and the like. Of these, substituted or unsubstituted amino groups, epoxy groups, isocyanate groups, isocyanurates and the like are preferable because they have a high adhesiveness improving effect, and amino groups are particularly preferable.

A silane coupling agent having both a hydrolyzable silicon group and an amino group is generally called aminosilane, but in the present invention, aminosilane also exhibits a function as a curing catalyst. Therefore, in the present specification, a specific example of aminosilane is described in the description of the curing catalyst. If it is desired to exert the function as an adhesive-imparting agent more, aminosilane may be used in an amount larger than the required amount as a curing catalyst.

Specific examples of silane coupling agents other than aminosilane include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl). Isocyanates such as trimethoxysilane and (isocyanatemethyl) dimethoxymethylsilane; ketimine-type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine; γ- Mercaptosilanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy Epoxysilanes such as silane; carboxy such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Silanes; Vinyl-type unsaturated group-containing isocyanates such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane; γ-chloropropyltrimethoxysilane, etc. Halogen-containing silanes; Isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate can be mentioned. Further, the above-mentioned reaction product of aminosilane and epoxysilane, reaction product of aminosilane and isocyanatesilane, reaction product of aminosilane and (meth) acryloyloxy group-containing silane, and the like can also be used. 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 derivatives obtained by modifying these, can also be used as the silane coupling agent. ..

The above silane coupling agent may be used alone or in combination of two or more.

The amount of the silane coupling agent used in the present invention is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the polymer (A) and the polymer (B) are used. ) Is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, and particularly preferably about 1 to 7 parts by weight, based on 100 parts by weight. If the blending amount is less than this range, sufficient adhesiveness may not be obtained. If the blending amount exceeds this range, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently.

In addition to the above-mentioned silane coupling agent, the adhesive-imparting agent is not particularly limited, and for example, epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate and the like can be used. The adhesive-imparting agent may be used alone or in combination of two or more.

In addition, silicate can be used in the composition 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 cured product obtained from the curable composition of the present invention. 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 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100. It is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkylsilicates) such as silane, 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 restorability, durability, and creep resistance of the present invention is greater than that of tetraalkoxysilane.

Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to the tetraalkoxysilane by a 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.).

(filler)
A filler can be added to the composition of the present invention. Fillers include reinforcing fillers such as fume silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic anhydride, hydrous silicic acid, and carbon black; heavy calcium carbonate, calcium glue carbonate, magnesium carbonate. , Silicic acid, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, active zinc flower, silas balloon, glass microballoon, phenol resin and vinylidene chloride Fillers such as resin powders such as organic microballoons of resin, PVC powder, PMMA powder; fibrous fillers such as glass fibers and filaments can be mentioned. When a filler is used, the amount used is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is used. 1 to 250 parts by weight is preferable with respect to 100 parts by weight, and 10 to 200 parts by weight is more preferable.

As described in Japanese Patent Application Laid-Open No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left to stand for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved, especially in the case of a one-component composition.

Further, when a highly transparent composition is obtained, as described in JP-A-11-302527, a polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as a filler. Further, as described in JP-A-2000-38560, a highly transparent composition can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Obtainable. The surface of the silicon dioxide fine powder generally has a silanol group (-SiOH), but (-SiO-hydrophobic group) is generated by reacting this silanol group with an organic silicon halide, an alcohol, or the like. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, and the like are reactively bonded to a silanol group existing on the surface of silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of a silanol group (-SiOH) is called a hydrophilic silica fine powder.

When it is desired to obtain a high-strength cured product by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic acid anhydride, hydrous silicic acid and carbon black, and surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, active zinc flower and the like is preferable, and when 100 parts by weight of the polymer (A), the polymer (A) and the polymer (B) are contained, the polymer ( Preferred results can be obtained by using 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of A) and the polymer (B). 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. 100 parts by weight of the polymer (A), and 100 parts by weight of the total amount of the polymer (A) and the polymer (B) when the polymer (A) and the polymer (B) are contained in the filler selected from the above. If 5 to 200 parts by weight is used, favorable 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 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.

It is preferable to add an organic balloon or an inorganic balloon in order to improve the workability (sharpness, etc.) of the 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, 5 to 300 μm is preferable.

The composition of the present invention is an adhesive for joints and exterior wall tiles of houses such as sizing boards, especially ceramic sizing boards, and adhesives for exterior wall tiles because the cured product has good chemical resistance. It is preferably used for tiles where the adhesive remains as it is, but it is desirable that the design of the outer wall and the design of the sealing material are in harmony. 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 the composition of the present invention contains a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, the cured product is in harmony with such a luxurious outer wall. However, due to its excellent chemical resistance, the appearance of this cured product is an excellent composition that lasts for a long period of time. When a granular substance is used, the surface has a sand-like or sandstone-like 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 to 5.0 mm, and an appropriate size is used according to the material, pattern, etc. of the outer wall. Those having a thickness of about 0.2 mm to 5.0 mm and those having a thickness of about 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 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.

About 1 to 200 parts by weight of the scaly or granular substance is blended with respect to 100 parts by weight of the composition such as the sealant composition and the adhesive composition. 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, and inorganic substances such as synthetic rubber, synthetic resin and alumina are used. In order to enhance the design when the joint is filled, it is colored in an appropriate color according to the material, pattern, etc. of the outer wall.

Preferred finishing methods and the like are described in JP-A-9-53063.

Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface has a sandbox-like or sandstone-like grainy feeling, and the weight can be reduced. The preferable diameter, blending amount, material and the like of the balloon are as follows as described in Japanese Patent Application Laid-Open No. 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, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran. , Inorganic materials and organic materials can be combined, 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 is processed or coated, or a balloon whose surface is 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 a silane coupling 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 thickness of about 0.2 mm to 5.0 mm and those having a thickness of about 0.5 mm to 5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and may not exhibit a grainy feeling. 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 composition in the range of 5 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 is adhered. The basic performance of the agent tends to be impaired. The volume concentration in which the balance with the basic performance of the sealing material is particularly preferable is 8 to 22 vol%.

When using a balloon, 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 make the surface matte. Amine compounds for the state, especially primary and / or secondary amines having a melting point of 35 ° C. or higher, can be added.

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, JP-A-10. It is described in JP-A-251618, JP-A-2000-154368, JP-A-2001-164237, WO97 / 05201 and the like.

Further, 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 this composition, the gas pressure inside the shell of the heat-expandable fine-grained hollow body increases, and the polymer outer shell material softens, dramatically expanding the volume and forming the adhesive interface. It plays a role of peeling. By adding 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.

Even when the composition of the present invention contains cured material particles of a sealing material, the cured product can form irregularities on the surface to improve the design. The preferable diameter, blending amount, material and the like of the cured material particles of the sealing material are as follows as described in Japanese Patent Application Laid-Open No. 2001-115142. The diameter is preferably 0.1 mm to 1 mm, more preferably about 0.2 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.

(Plasticizer)
A plasticizer can be added to the composition of the present invention. By adding the plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as the tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutylphthalate, diheptylphthalate, bis (2-ethylhexyl) phthalate and butylbenzylphthalate; non-fragrances such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate. Group dibasic acid esters; aliphatic esters such as butyl oleate and methyl acetyllicylinolate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; alkyldiphenyl , Partially hydrogenated tarphenyl, and other hydrocarbon-based oils; process oils; epoxidized soybean oil, benzyl epoxy stearate and other epoxy plasticants.

Moreover, a polymer plasticizer can be used. When a high molecular weight plasticizer is used, the initial physical properties can be maintained for a long period of time as compared with the case where a low molecular weight 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 1000 or more polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or a derivative such as a derivative obtained by converting the hydroxyl group of these polyether polyols into an ester group, an ether group, etc .; Polystyrenes such as styrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like can be mentioned, but the present invention is not limited thereto.

Among these polymer plasticizers, when the polymer (A), the polymer (A) and the polymer (B) are contained, the one that is compatible with the polymer (A) and the polymer (B) 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.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000 to 3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rainfall, and the initial physical properties cannot be maintained for a long period of time, causing contamination due to dust adhesion and the like, and the alkyd coating property cannot be improved. Further, 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 and less than 1.80. 1.70 or less is more preferable, 1.60 or less is still more preferable, 1.50 or less is further preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

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

Further, the polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it can act as a reactive plasticizer and prevent the transfer of the plasticizer from the cured product. When having a reactive silicon group, the average number of groups per molecule is preferably 1 or less, and more preferably 0.8 or less. When a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, is used, its number average molecular weight contains the polymer (A), the polymer (A) and the polymer (B). In this case, it is preferably lower than the polymer (A) and the polymer (B). Otherwise, the plasticizing effect may not be obtained.

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. It should be noted that these plasticizers can also be blended at the time of polymer production.

The amount of the plasticizer used is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. On the other hand, 5 to 150 parts by weight is preferable, 10 to 120 parts by weight is more preferable, and 20 to 100 parts by weight is further preferable. 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.

(Adhesive-imparting resin)
A tackifier can be added to the composition of the present invention. The adhesiveness-imparting resin is not particularly limited, but any resin normally used at room temperature, whether solid or liquid, can be used. Specific examples include styrene-based block copolymers, their hydrocarbons, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resins, tall oil-modified phenolic resins, etc.), terpenephenolic resins, xylene-phenolic resins, cyclos. Pentaziene-phenol resin, kumaron inden resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpen-based resin, DCPD resin petroleum resin, etc. can be mentioned. These may be used alone or in combination of two or more. Examples of the styrene-based block copolymer and its hydrogen additive include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), and a styrene-ethylenebutylene-styrene block copolymer. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS) and the like. The adhesive-imparting resin may be used alone or in combination of two or more.

The tackifying resin contains 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. , Preferably 5 to 1,000 parts by weight, more preferably 10 to 100 parts by weight.

(Solvent or diluent)
Solvents or diluents can be added to the compositions of the present invention. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers and the like can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher, due to the problem of air pollution when the composition is used indoors. .. The above solvent or diluent may be used alone or in combination of two or more.

(Physical characteristic adjuster)
If necessary, a physical property adjusting agent for adjusting the tensile properties of the cured product produced may be added to the curable composition of the present invention. The physical property adjusting agent is not particularly limited, but for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy. Examples thereof include alkoxysilanes having an unsaturated group such as alkylisopropenoxysilanes such as silanes, vinyltrimethoxysilanes and vinyldimethylmethoxysilanes; silicone varnishes; polysiloxanes and the like. By using the physical property adjusting agent, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be decreased to achieve elongation at break. The above-mentioned physical property adjusting agent may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has an action of lowering the modulus of the cured product without aggravating the stickiness of the surface of the cured product. Particularly, a compound that produces trimethylsilanol is preferable. 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, a compound that is a derivative of an alkyl alcohol such as hexanol, octanol, and decanol and _{that produces a silicon compound that produces R 3} SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029. Examples thereof include compounds which are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol or sorbitol and _{which produce silicon compounds such as trimethylsilanol which produce R 3 SiOH by hydrolysis.}

Further, a compound which is a derivative of an oxypropylene polymer as described in JP-A-7-258534 and which produces a silicon compound which produces _{R 3 SiOH such as trimethylsilanol by hydrolysis can also be mentioned.} Further, a polymer having a crosslinkable hydrolyzable silicon-containing 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 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. It can be preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

(Tixo property imparting agent)
If necessary, a ticking property-imparting agent (anti-dripping agent) may be added to the curable composition of the present invention in order to prevent dripping and improve workability. 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 size of 10 to 500 μm as described in JP-A-11-349916 or an organic fiber as described in JP-A-2003-155389 is used, the thixophilicity is high. A composition having good workability can be obtained. These thixogenicity-imparting agents (anti-dripping agents) may be used alone or in combination of two or more. The thixophilicity-imparting agent is based on 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. , Preferably 0.1 to 20 parts by weight can be used.

(Compound containing epoxy group)
In the composition 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 epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized flax 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. When the epoxy compound contains 100 parts by weight of the polymer (A), the polymer (A) and the polymer (B), the total amount of the polymer (A) and the polymer (B) is 0. It is best to use in the range of 5 to 50 parts by weight.

(Photocurable substance)
A photocurable substance can be used in the composition of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance in which a molecular structure undergoes a chemical change in a considerably short time due to the action of light, resulting in a physical change such as curing. 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, polyvinyl chlorides, azide resins and the like can be used. The unsaturated acrylic compound is a monomer, an oligomer or a mixture thereof having one or several acrylic or methacrylic unsaturated groups, and is 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. Examples thereof include -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325 and (polyfunctional) Aronix M-400, which particularly contain an acrylic functional group. Compounds are preferable, and compounds containing an average of 3 or more homofunctional groups in one molecule are preferable. (All of Aronix are products of Toagosei Chemical Industry Co., Ltd.).

Examples of vinyl polysilicates include photosensitive resins having a cinnamoyl group as a photosensitive group and esterified polyvinyl alcohol with cinnamic acid, as well as 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). Publication, published by the Publishing Department of the Printing Society, pp. 93-, pp. 106-, pp. 117-). Can be done. 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 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight can be used more preferably. If the amount of the photocurable substance used is 0.1 parts by weight or less, the effect of increasing the weather resistance may not be obtained, and if it is 20 parts by weight or more, the cured product becomes too hard and tends to crack.

(Oxygen curable substance)
An oxygen-curable substance can be used in the composition of the present invention. An example of an unsaturated compound that can react with oxygen in the air is an oxygen-curable substance that reacts with oxygen in the air to form a cured film near the surface of the cured product, which causes stickiness on the surface and dust on the surface of the cured product. It acts to prevent the adhesion of dust and dirt. Specific examples of the oxygen-curable substance include dry oils such as diene oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with the dry oils. , Silicon resin; polymers of 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers such as NBR and SBR obtained by copolymerizing a liquid polymer or a monomer such as acrylonitrile or styrene having copolymerizability with these diene compounds so that the diene compound is the main component. Further, various modified products thereof (polymerized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, vernicia 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 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 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100% by weight. It is preferably used in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

(Antioxidant)
Antioxidants (antioxidants) can be used in the compositions of the present invention. The use of an antioxidant can increase the heat resistance of the cured product. Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based, but hindered phenol-based agents are particularly preferable. Similarly, Chinubin 622LD, Chinubin 144, CHIMASSORB944LD, CHIMASORB119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.). All of the above are manufactured by Asahi Denka Kogyo Co., Ltd.); The indicated hindered amine light stabilizers 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 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. It is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

(Light stabilizer)
A light stabilizer can be used in the composition of the present invention. The use of a light stabilizer can prevent photooxidation deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, but hindered amine-based compounds are particularly preferable. The amount of the light stabilizer used is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. It is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts 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 composition of the present invention, particularly when an unsaturated acrylic compound is used, as described in JP-A-5-70531, a tertiary amine-containing hindered amine is used as a hindered amine-based light stabilizer. It is preferable to use a system light stabilizer for improving the storage stability of the composition. As the tertiary amine-containing hindered amine-based light stabilizers, Tinubin 622LD, Tinubin 144, CHIMASSORB119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (all above). (All manufactured by Asahi Denka Kogyo Co., Ltd.); Photostabilizers such as Chinubin LS-765, LS-292, LS-266, LS-1114, LS-744 (all manufactured by Sankyo Co., Ltd.) can be exemplified.

(UV absorber)
An ultraviolet absorber can be used in the composition of the present invention. The use of UV absorbers can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. It is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts 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.

(Epoxy resin)
Epoxy resin can be added to the composition of the present invention. The composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly an adhesive for outer wall tiles. Examples of the epoxy resin include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame-retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol A. Glycidyl ether type epoxy resin with propylene oxide adduct, p-oxybenzoate glycidyl ether type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerin, hydrandin type epoxy resin, petroleum resin, etc. Examples thereof include epoxidized products of unsaturated polymers, but the present invention is not limited to these, and commonly used epoxy resins can be used. Those containing at least two epoxy groups in the molecule are preferable because they have high reactivity during curing and the cured product easily forms a three-dimensional network. More preferable ones include bisphenol A type epoxy resins and novolak type epoxy resins. When these epoxy resins and the polymer (A), or the polymer (A) and the polymer (B) are contained, the usage ratio of the total amount of the polymer (A) and the polymer (B) is the weight ratio. ((A) or (A) + (B)) / epoxy resin = 100/1 to 1/100 is preferable. When the ratio of ((A) or (A) + (B)) / epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin product, and ((A)). Or, if the ratio of (A) + (B)) / epoxy resin exceeds 100/1, the strength of the cured organic polymer tends to be insufficient. The preferable usage ratio cannot be unconditionally determined because it varies depending on the use of the curable resin composition and the like, but for example, when improving the impact resistance, flexibility, toughness, peeling strength, etc. of the cured epoxy resin composition. When the polymer (A) or the polymer (A) and the polymer (B) are contained in 100 parts by weight of the epoxy resin, the total amount of the polymer (A) and the polymer (B) is 1 to 1. It is preferably 100 parts by weight, more preferably 5 to 100 parts by weight. On the other hand, when improving the strength of the cured product of the polymer (A) component, 100 parts by weight of the polymer (A), or when containing the polymer (A) and the polymer (B), the polymer ( It is preferable to use 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of the epoxy resin with respect to 100 parts by weight of the total amount of A) and the polymer (B).

When an epoxy resin is added, it is natural that a curing agent that cures the epoxy resin can be used in combination with the composition of the present invention. The epoxy resin curing agent that can be used is not particularly limited, and a generally used epoxy resin curing agent can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidin, m-xylylene diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly. Primary and secondary amines such as ethers; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Classes; dicyandiamides; boron trifluoride complex compounds; phthalic anhydrides, hexahydrophthalic anhydrides, tetrahydrophthalic anhydrides, dodecinyl anhydrides, pyromellitic anhydrides, chlorenic anhydrides and the like; alcohols Compounds such as, but not limited to, phenols; carboxylic acids; diketone complex compounds of aluminum or zirconium can be exemplified. Further, the curing agent may be used alone or in combination of two or more.

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

Ketimine can be used as a curing agent for the epoxy resin. Ketimine exists stably in the absence of moisture, is decomposed into primary amines and ketones by moisture, and the generated primary amine becomes a room temperature curable curing agent for epoxy resins. A one-component composition can be obtained by using ketimine. Such ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

Known amine compounds and carbonyl compounds may be used for the synthesis of ketimine. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, etc. Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino) Polyvalent amines such as ethyl) amines and tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyltriethoxysilane, N- (β) Aminosilanes such as −aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; and the like can be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone. , Methyl ethyl ketone, Methyl propyl ketone, Methyl isopropyl ketone, Methyl isobutyl ketone, diethyl ketone, Dipropyl ketone, Diisopropyl ketone, Dibutyl ketone, Diisobutyl ketone and other aliphatic ketones; , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane; and the like can be used.

When an imino group is present in ketimine, the imino group may be reacted with a styrene oxide; a glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; a glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and 1 to 100 parts by weight can be used with respect to 100 parts by weight of the epoxy resin, and the amount used is the type of epoxy resin and ketimine. Can be set as appropriate.

(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 can be added to the curable composition of the present invention. The flame retardant may be used alone or in combination of two or more.

The flame retardant is preferably 100 parts by weight based on 100 parts by weight of the polymer (A), and when containing the polymer (A) and the polymer (B), the total amount of the polymer (A) and the polymer (B) is 100 parts by weight. Is used in an amount of 5 to 200 parts by mass, more preferably 10 to 100 parts by mass.

(Other additives)
Various additives may be added to the curable composition of the present invention, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, foaming agents and anti-termite agents. , Antifungal agents, etc. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives given in the present specification include, for example, Tokusei No. 4-69659, Tokusei 7-108928, JP-A-63-254149, JP-A-64-22904, and Special Publication No. It is described in each publication of Kai 2001-72854 and the like.

<Preparation of curable composition>
The curable composition of the present invention can be prepared as a one-component type in which all the compounding components are compounded and sealed in advance and cured by the moisture in the air after construction, and a curing catalyst and a filler are separately used as a curing agent. , Plasticizer, water and other components can be blended and prepared as a two-component type in which 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 either dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and 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 silicon group, so that gelation occurs even if some water is contained in the compounding agent. However, if long-term storage stability is required, dehydration drying is preferable. As a dehydration and drying method, a heat drying method is preferable for a solid substance such as powder, a vacuum dehydration method for a liquid substance, or a dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is preferable. be. Further, a small amount of the isocyanate compound may be blended and the isocyanate group may be reacted with water for dehydration. Alternatively, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water to dehydrate. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl. Storage stability is further improved by adding an alkoxysilane compound such as methyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane.

The amount of the dehydrating agent, especially the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 100 parts by weight of the polymer (A), and when the polymer (A) and the polymer (B) are contained, the polymer (A) is used. ) And the polymer (B) in an amount of 100 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

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

When the curable composition 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.

<Use>
The curable composition of the present invention is an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a molding agent, a vibration damping material, a vibration damping material, a soundproofing material, a foam material, a paint, a spraying material. Can be used for such as. The cured product obtained by curing the curable composition 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 insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact adhesives, spray sealants, crack repair materials, and tiles. Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical equipment sealants, food packaging materials, sealing materials for exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, heat conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and rust-proof / waterproof encapsulants for wire-reinforced glass and laminated glass end faces (cut parts), It can be used for various purposes such as liquid sealants used in automobile parts, electric parts, various machine parts, and the like. In addition, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., alone or with the help of primers, and can be used as various types of sealing and adhesive compositions. .. Further, the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, direct glazing sealants, double glazing sealants, SSG method sealants, or building working joint sealants, It can also be used as.

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

The fluorination rate in the examples was calculated from the result of ¹ H-NMR measurement by dissolving in deuterated chloroform using AVANCE III HD500 manufactured by Bruker. When the dimethoxymethylsilyl group-terminated polyoxyalkylene polymer is fluorinated, the fluorination rate can be accurately determined by ^{1 1 H-NMR.} Specifically, when the methoxy group on silicon is modified to a fluoro group, the peak of the methyl group on silicon shifts, so that the difluoromethylsilyl group and monofluoromethoxymethylsilyl group in the polymer (A), Since the molar ratio of the dimethoxymethylsilyl group can be calculated, the fluorination rate can be calculated.

The viscosity in the examples was measured at 23 ° C. and a relative humidity of 50% using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., measuring cone: 3 ° C × R14).

The appearance in the examples is based on the Gardner color number test method (JIS K 0071-2), and the Gardner color number prepared using potassium hexachloroplatinum (IV), iron (III) chloride, cobalt (II) chloride, and hydrochloric acid. The standard solution and the transmitted color of the sample were visually compared and measured. In Table 1, it was described as colorless when it was colorless or slightly colored less than the G-1 standard solution, and colored when it was clearly colored more than the G-1 standard solution.

(Synthesis Example 1)
Using polyoxypropylene glycol having a number average molecular weight of about 4500 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 14,300 having hydroxyl groups at both ends, and the molecular weight distribution is Mw / Mn. = 1.21 polyoxypropylene was obtained. To the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the polymer to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. The obtained unpurified polyoxypropylene is mixed with n-hexane and water, and then the water is removed by centrifugation, and hexane is devolatile from the obtained hexane solution under reduced pressure to remove the metal salt in the polymer. Removed. From the above, polyoxypropylene having an allyl group at the terminal was obtained. To 100 parts by weight of this polymer, 50 ppm of a platinum divinyldisiloxane complex solution (3% by weight of platinum equivalent isopropanol solution) was added, and 1.7 parts by weight of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (B-1) having a number average molecular weight of 14,600 having a dimethoxymethylsilyl group at the terminal. rice field. It was found that the polymer (B-1) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.5 in one molecule.

(Example 1)
To 100 parts by weight of the dimethoxymethylsilyl group-terminated polyoxypropylene-based polymer (B-1), 5 parts of methanol was added and stirred. BF ₃ methanol complex _(BF 3 · 2 MeOH) 0.94 parts by weight was added dropwise slowly according to the following table of the formulation under a stream of nitrogen, the internal temperature of the reaction solution was allowed to react for 3 hours at 38 ° C.. _{Evaporate under reduced pressure so that the internal pressure is 5 Torr or less, remove methanol and BF 3} derived components until the residual methanol amount is 3000 ppm or less by GC measurement, and the number average molecular weight containing Si—F bond is 15,000. A silicon group-containing polyoxypropylene-based polymer (A-1) was obtained. ^{1 By 1} H-NMR measurement, the molar ratio of Si-F bonds to the total number of moles of Si-F bonds and Si-OMe bonds in the polymer (referred to as fluorination rate in the following text and in the table) is 67. Confirmed to be%. A 10 mL polymer (A-1) was placed in a transparent glass vial having a capacity of 20 mL, filled with nitrogen, the cap was closed, and the mixture was stored at 80 ° C. for 1 week to examine changes in viscosity and appearance. The results are shown in Table 1 below.

(Example 2)
BF ₃ except that the amount of methanol complex _(BF 3 · 2 MeOH) was 0.99 parts by weight in the same manner as in Example 1, the number-average molecular weight 15 containing Si-F bonds is a fluorination rate 71% A silicon-containing polyoxypropylene-based polymer (A-2) of 000 was obtained. In the same manner as in Example 1, the polymer (A-2) was stored at 80 ° C., and the changes in viscosity and appearance and the presence or absence of foul odor were examined. The results are shown in Table 1 below.

(Example 3)
BF ₃ except that 1.16 parts by weight amount of methanol complex _(BF 3 · 2 MeOH) in the same manner as in Example 1, Si-F bonds having a number average molecular weight of 15,000 is a fluorination rate 86% A silicon group-containing polyoxypropylene-based polymer (A-3) containing the above was obtained. In the same manner as in Example 1, the polymer (A-3) was stored at 80 ° C., and the changes in viscosity and appearance and the presence or absence of foul odor were examined. The results are shown in Table 1 below.

(Example 4)
BF ₃ except that the amount of methanol complex _(BF 3 · 2 MeOH) was 1.26 parts by weight in the same manner as in Example 1, Si-F bonds having a number average molecular weight of 15,000 is 90% fluorination rate A silicon group-containing polyoxypropylene-based polymer (A-4) containing the above was obtained. In the same manner as in Example 1, the polymer (A-4) was stored at 80 ° C., and the changes in viscosity and appearance and the presence or absence of foul odor were examined. The results are shown in Table 1 below.

(Comparative Example 1)
BF ₃ except that the amount of methanol complex _(BF 3 · 2 MeOH) was 0.70 parts by weight in the same manner as in Example 1, Si-F bonds having a number average molecular weight of 15,000 is 50% fluorination rate A silicon group-containing polyoxypropylene-based polymer (A-5) containing the above was obtained. In the same manner as in Example 1, the polymer (A-5) was stored at 80 ° C., and the changes in viscosity and appearance and the presence or absence of foul odor were examined. The results are shown in Table 1 below.

(Comparative Example 2)
BF ₃ except that the amount of methanol complex _(BF 3 · 2 MeOH) was 1.54 parts by weight in the same manner as in Example 1, a number average molecular weight containing Si-F bonds fluorination rate> 99% 15,000 silicon-containing polyoxypropylene-based polymers (A-6) were obtained. In the same manner as in Example 1, the polymer (A-6) was stored at 80 ° C., and the changes in viscosity and appearance and the presence or absence of foul odor were examined. The results are shown in Table 1 below.

(Synthesis Example 2)
22.0 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 ° C. under a nitrogen atmosphere. There, 0.6 parts by weight of methyl methacrylate, 81.0 parts by weight of butyl acrylate, 15.0 parts by weight of stearyl methacrylate, 3.4 parts by weight of 3-mercaptopropyldimethoxymethylsilane, and 2,2'-azobis (2-). A mixed solution prepared by dissolving 0.35 parts by weight of methylbutyronitrile) in 17.5 parts by weight of isobutanol was added dropwise over 5 hours. Further, polymerization was carried out at 105 ° C. for 1.5 hours, and the polyacrylic polymer of the obtained isobutanol solution was removed under heating and reduced pressure to remove isobutanol, whereby 0.9 dimethoxys were averaged in one molecule. A poly (meth) acrylic acid ester polymer (B-2) having a methylsilyl group, having a number average molecular weight of 4,300 and a weight average molecular weight of 8,300 was obtained.

(Reference example 1)
To 100 parts by weight of the dimethoxysilyl group-terminated acrylic ester-based polymer (B-2), 5 parts of methanol was added and stirred. BF ₃ methanol complex _(BF 3 · 2 MeOH) 2.27 parts by weight was added dropwise slowly according to the following table of the formulation under a stream of nitrogen, the internal temperature of the reaction solution was allowed to react for 3 hours at 38 ° C.. _{Evaporate under reduced pressure so that the internal pressure is 5 Torr or less, remove methanol and BF 3} derived components until the residual methanol amount is 3000 ppm or less by GC measurement, and the number average molecular weight containing Si—F bond is 4, 700 silicon group-containing acrylic acid ester-based polymer (A-7) was obtained. ^{1 The} disappearance of the peak derived from the raw material was confirmed by 1 H-NMR measurement. That is, it was confirmed that the fluorination rate was> 99%. Similar to Example 1, (A-7) was stored at 80 ° C. and examined for changes in viscosity and appearance and the presence or absence of foul odor. As a result, no coloring, thickening and foul odor were confirmed.

In Examples 1-4 in which the fluorination rate was 60 to 90%, no obvious coloring was observed in the appearance at 80 ° C. for 1 week, there was no foul odor, and the viscosity did not exceed 50 Pa · s. In Comparative Example 1 in which the fluorination rate was small, large thickening occurred after storage and exceeded 50 Pa · s. In Comparative Example 2 having a large fluorination rate, the appearance was colored both immediately after synthesis and after storage, and a foul odor was generated.
In Reference Example 1 using the acrylic ester-based polymer, there were no problems of coloring and foul odor in spite of the fluorination rate of> 99%.

Claims (12)

A silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, which is a Si—F bond and a Si—Z bond (Z is a reactive group other than fluorine) in the total polymer. A silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, wherein the molar ratio of the Si—F bond to the total number of moles is 60 to 90%. The silicon group containing a Si-F bond according to claim 1, wherein the molar ratio of the Si—F bond to the total number of moles of the Si—F bond and the Si—Z bond in the total polymer is 70 to 85%. Containing polyoxyalkylene polymer (A). The silicon group containing the Si—F bond has the following general formula (1):
−SiF _a R ¹ _b Z _c (1)
(In the formula, R ¹ is an independently substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO− (R ² is independently substituted or substituted with 1 to 20 carbon atoms, respectively). Indicates any of the organosiloxy groups represented by) (is an unsubstituted hydrocarbon group). Z is an independently reactive group other than fluorine. A is any of 1, 2 and 3. b is either 0, 1, 2, c is any of 0, 1, 2, a + b + c If a 3 .b or c is 2, two ^{R 1} or two Z is The silicon group-containing polyoxyalkylene polymer (A) containing the Si—F bond according to claim 1 or 2, which is represented by the same or different from each other. The silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond according to any one of claims 1 to 3, which has a number average molecular weight of 3000 to 30,000. The silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond according to any one of claims 1 to 4, wherein Z in the general formula (1) is an alkoxy group. The silicon group-containing polyoxyalkylene polymer (A) containing the Si—F bond according to any one of claims 1 to 5, and the reactive silicon group-containing polymer (B) having no Si—F bond. A curable composition containing 0.01 to 50 parts by weight of the polymer (A) with respect to 100 parts by weight of the polymer (B). The curable composition according to claim 6, further containing a curing catalyst (C). The curable composition according to claim 7, wherein the curing catalyst (C) is an amine compound. A sealing material using the curable composition according to any one of claims 6 to 8. An adhesive made by using the curable composition according to any one of claims 6 to 8. A cured product obtained by curing the curable composition according to any one of claims 6 to 8. A method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond, wherein the reactive group of the reactive silicon group-containing polyoxyalkylene polymer is converted into a fluorine atom by a fluorinating agent. Then, the molar ratio of the Si—F bond to the total number of molars of the Si—F bond and the Si—Z bond (Z is a reactive group other than fluorine) in the total polymer is converted to 60 to 90%. A method for producing a silicon group-containing polyoxyalkylene polymer (A) containing a Si—F bond.