JP7489206B2 - Polymer containing Si-F bond and curable composition containing same - Google Patents

Description

The present invention relates to a silicon-containing polymer that contains a Si-F bond, and a curable composition that contains the polymer.

Polymers containing at least one reactive silicon group in the molecule are known to have the property of crosslinking through the formation of siloxane bonds accompanied by hydrolysis of the reactive silicon group by moisture, etc., even at room temperature, to give a rubber-like cured product.

Among these polymers containing reactive silicon groups, organic polymers whose main chain skeleton is a polyoxyalkylene polymer are already being produced industrially and are widely used in applications such as sealants, adhesives, and paints.

When these polymers are used as curable compositions for sealing materials, adhesives, coatings, etc., various properties are required, such as curability, adhesiveness, and mechanical properties of the cured product.

On the other hand, a silicon-containing polymer containing a Si-F bond and a curable composition containing the polymer are disclosed in Patent Document 1, and are known to have excellent curability without the use of an organotin catalyst and also to exhibit excellent rapid curing properties. Such curable compositions can be used in applications such as sealants, adhesives, and paints.

International Publication No. 2008/032539

The polymer having a silicon-containing polyoxyalkylene skeleton containing Si-F bonds, synthesized by the method described in Reference 1, has a tendency to produce black foreign matter during production, making processing difficult, and also has room for improvement in that it tends to produce coloration and an unpleasant odor after storage. The present invention aims to provide a moisture-curable polymer that has the property of being cured by moisture at room temperature and that exhibits rapid curing even without the use of an organotin catalyst, and a moisture-curable composition containing the same, with good storage stability.

In light of the above circumstances, the inventors conducted extensive research and discovered that the above problems could be solved by controlling 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 entire polymer, which led to the completion of the present invention.

That is, the present invention provides
(1) The present invention relates to a silicon group-containing polyoxyalkylene polymer (A) containing Si-F bonds, in which the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer is 60 to 90%.
The present invention also relates to (2) the silicon-containing polyoxyalkylene polymer (A) containing Si-F bonds as described in (1) above, in which the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds in the entire polymer is 70 to 85%.
Also, (3) the silicon group containing a Si—F bond is represented by the following general formula (1):
-SiF _a R ¹ _b Z _c (1)
(wherein R ¹ 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an organosiloxy group represented by R ² ₃ SiO- (wherein R ² 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms); each Z is independently a reactive group other than fluorine; a is 1, 2 or 3; b is 0, 1 or 2; c is 0, 1 or 2; and a+b+c is 3. When b or c is 2, the two R ¹ 's or the two Z's may be the same or different.)
The present invention also relates to (4) the silicon-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 3,000 to 30,000.
The present invention also relates to (5) the silicon-containing polyoxyalkylene polymer (A) 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.
The present invention also relates to (6) a curable composition comprising (A) a silicon group-containing polyoxyalkylene polymer having a Si-F bond according to any one of (1) to (5) above, and (B) a reactive silicon group-containing polymer having no Si-F bond, wherein the amount of the polymer (A) is 0.01 to 50 parts by weight per 100 parts by weight of the polymer (B).
The present invention also relates to (7) the curable composition according to the above (6), which further contains a curing catalyst (C).
The present invention also relates to (8) the curable composition according to the above (7), in which the curing catalyst (C) is an amine compound.
The present invention also relates to (9) a sealant obtained by using the curable composition according to any one of (6) to (8) above.
(10) The present invention relates to an adhesive obtained 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.
The present invention also relates to (12) a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing Si-F bonds, which comprises converting reactive groups of the reactive silicon group-containing polyoxyalkylene polymer to fluorine atoms with a fluorinating agent so that the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer is 60 to 90%.

The polymer and curable composition of the present invention have excellent curability even without the use of an organotin catalyst, and also have excellent storage stability. Such curing of the present invention can be suitably used for sealing materials and adhesives.

The present invention will be described in detail below. In this specification, the term "reactive silicon group" refers to a silicon-containing group that has a hydrolyzable group or a hydroxyl group bonded to a silicon atom and can crosslink by forming a siloxane bond, and the term "reactive group" refers to a hydrolyzable group or a hydroxyl group.

The silicon-containing polyoxyalkylene polymer (A) (also referred to as polymer (A)) containing Si-F bonds and the curable composition containing polymer (A) of the present invention exhibit curability in the presence of moisture even at room temperature.

The curable composition using the silicon group-containing polyoxyalkylene polymer (A) containing Si-F bonds of the present invention in combination with the polymer (B) (also referred to as polymer (B)) having reactive silicon groups but no Si-F bonds is characterized by exhibiting faster curing properties than the use of only the polymer (B) containing reactive silicon groups but no Si-F bonds.

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

(Silicon Group Containing Si-F Bond)
The Si-F bond of polymer (A) is effective wherever it is located in the polymer molecule, and is represented by -SiR' ₂ F if it is at the end of the main chain or side chain, and by -SiR'F- or ≡SiF (each R' is independently F or any group) if it is incorporated in the main chain of the polymer.

The silicon group having a Si—F bond at the end of the main chain or side chain is represented by the following general formula (1):
-SiF _a R ¹ _b Z _c (1)
(In the formula, R ¹ 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an organosiloxy group represented by R ² ₃ SiO- (R ² 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms). Each Z is independently a reactive group other than fluorine. a is 1, 2 or 3; b is 0, 1 or 2; c is 0, 1 or 2; and a+b+c is 3. When b or c is 2, the two R ¹ 's or the two Z's may be the same or different.)

Reactive groups other than fluorine represented by Z in general formula (1) include hydroxyl groups, halogen atoms other than fluorine, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. Among these, hydroxyl groups, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, hydroxyl groups and alkoxy groups are more preferred, and alkoxy groups are particularly preferred from the viewpoint of mild hydrolysis and ease of handling.

Specific examples of ^R1 include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and _{triorganosiloxy groups represented by R23SiO-} ⁱⁿ which ^R2 is a methyl group, phenyl group, etc. Of these, a methyl group is particularly preferred.

Specific examples of silicon groups represented by general formula (1) include silicon groups that have no reactive groups other than fluorine, such as a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, a fluorodiphenylsilyl group, a fluorodibenzylsilyl group, a difluoromethylsilyl group, a difluoroethylsilyl group, a difluorophenylsilyl group, a difluorobenzylsilyl group, a trifluorosilyl group, and a difluoro(methoxymethyl)silyl group; and silicon groups that have both fluorine and other reactive groups, such as a fluoromethoxymethylsilyl group, a fluoroethoxymethylsilyl group, a fluoromethoxyethylsilyl group, a fluoromethoxyphenylsilyl group, a fluorodimethoxysilyl group, a fluorodiethoxysilyl group, a fluorodipropoxysilyl group, a fluorodiphenoxysilyl 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. From the viewpoint of ease of synthesis, a fluorodimethylsilyl group, a difluoromethylsilyl group, a trifluorosilyl group, a fluoromethoxymethylsilyl group, a fluoroethoxymethylsilyl group, a fluoromethoxyethylsilyl group, a fluorodimethoxysilyl group, and a fluorodiethoxysilyl group are more preferred, a fluorodimethylsilyl group, a fluoromethoxymethylsilyl group, a fluorodimethoxysilyl group, and a fluorodiethoxysilyl group are particularly preferred, and a fluoromethoxymethylsilyl group is the most preferred.

Examples of silicon groups having a Si--F bond that are incorporated into the main chain of a polymer include --Si(CH ₃ )F--, --Si(C ₆ H ₅ )F--, --SiF ₂ --, and .tbd.SiF.

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, more preferably 0.7 to 5.0, and even more preferably 1.0 to 4.0. Furthermore, it is also possible to use a polymer (A) having an average of more than one reactive silicon group per terminal.

When using the polymer (A) of the present invention, that is, in the curable composition of the present invention, the above-mentioned various polymers (A) containing Si-F groups may be used alone or in combination of two or more kinds.

(Main chain skeleton)
The polyoxyalkylene polymer which is the main chain skeleton of the polymer (A) is represented by the general formula (2):
-R ³ -O- (2)
(wherein ^R3 is a linear or branched alkylene group having 1 to 14 carbon atoms), and ^R3 in general formula (2) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by general formula (2) are:

The main chain skeleton 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, a polymer consisting mainly of a polyoxypropylene-based polymer is preferred because it 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 preferably carried out by converting the silicon group of a reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine into a silicon group containing a Si-F bond.

As a method for producing a reactive silicon group-containing polyoxyalkylene polymer having a reactive group other than fluorine, the following are preferred: (i) a method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst, the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene polymer is converted to a carbon-carbon unsaturated group, and a silane compound is added by a hydrosilylation reaction; (ii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst, the obtained hydroxyl-terminated polyoxyalkylene polymer is reacted with a compound having both a group reactive with a hydroxyl group and a reactive silicon group; and (iii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is reacted with an excess polyisocyanate compound to form a polymer having an isocyanate group at the end, and then a compound having both a group reactive with an isocyanate group and a reactive silicon group is reacted.

Examples of initiators having a hydroxyl group that can be used in methods (i) and (ii) include initiators having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, polyoxypropylene monoallyl ether, and polyoxypropylene monoalkyl ether.

The epoxy compounds used in 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. Among these, propylene oxide is preferred.

The carbon-carbon unsaturated group used in method (i) includes a vinyl group, an allyl group, a methallyl group, a propargyl group, and the like. Of these, the allyl group is preferred.

As a method for converting the hydroxyl groups in (i) to carbon-carbon unsaturated groups, it is preferable to use a method in which an alkali metal salt is reacted with a polymer containing hydroxyl groups at its ends, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted therewith.

Examples of halogenated hydrocarbon compounds used in method (i) include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, vinyl iodide, allyl iodide, methallyl iodide, and propargyl iodide.

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

The hydrosilylation reaction used in the method (i) can be accelerated by the use of various catalysts. As the hydrosilylation catalyst, any known catalyst may be used. For example, platinum supported on a carrier such as alumina, silica, or carbon black, chloroplatinic acid, chloroplatinic acid complexes consisting of chloroplatinic acid and alcohols, aldehydes, ketones, or the like, platinum-olefin complexes [e.g., Pt( _CH2 = _CH2 ) ₂ ( _PPh3 ), Pt( _CH2 = _CH2 ) _2Cl2 ], platinum-vinylsiloxane complexes [ _Pt {(vinyl) _Me2SiOSiMe2 (vinyl)}, Pt{Me(vinyl)SiO} ₄ ], platinum-phosphine complexes [Ph( _PPh3 ) ₄ , Pt( _PBu3 ) ₄ ], platinum-phosphite complexes [Pt{P(OPh) ₃ } ₄ ] _, and the like can be used.

Examples of compounds having both a group reactive with a hydroxyl group and a reactive silicon group that can be used in method (ii) include isocyanate silanes such as 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl dimethoxy methyl silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, and isocyanate methyl dimethoxy methyl silane; mercapto silanes such as 3-mercapto propyl trimethoxy silane, 3-mercapto propyl dimethoxy methyl silane, and 3-mercapto propyl triethoxy silane; and epoxy silanes such as 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl dimethoxy methyl silane, and 3-glycidoxy propyl triethoxy silane.

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

Compounds having both a group reactive with an isocyanate group and a reactive silicon group that can be used in the method (iii) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, γ-(N-phenyl)aminopropyl Examples of such silanes include amino group-containing silanes such as propyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as gamma-hydroxypropyltrimethoxysilane and gamma-hydroxypropyldimethoxymethylsilane; mercapto group-containing silanes such as gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyldimethoxymethylsilane; and the like.

As a method for converting the silicon groups of the resulting reactive silicon group-containing polyoxyalkylene polymer having reactive groups other than fluorine to silicon groups containing Si-F bonds, it is preferable to use various fluorinating agents.

Specific examples of fluorinating agents include _NH4F , HF, _BF3 , etc., but from the viewpoint of reaction simplicity, efficiency, safety, etc., fluorination of alkoxysilyl groups using _BF3 is preferred. As _BF3 , _BF3 gas, _BF3 ether complex, _BF3 amine complex, _BF3 alcohol complex, _BF3 carboxylic acid complex, etc. can be used, but fluorination of alkoxysilyl groups using _BF3 methanol complex is preferred because it does not generate salts as by-products and is easy to post-process. In addition, it is preferable to use _BF3 methanol complex because the reaction does not require heating, etc., and fluorination proceeds easily even at room temperature, and it is more preferable to use one with coordination number 2 represented by the chemical formula _BF3.2MeOH .

The polymer (A) in the present invention is characterized in that the molar ratio of Si-F bonds (also called the fluorination rate) to the total number of moles of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer 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 moles of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer (A) is 60% or more, the reactive groups on the silicon groups remaining in the polymer (A) crosslink, which solves the problem of increased viscosity and difficulty in 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 entire polymer (A) is 90% or less, the problems of yellow coloration and loss of transparency during storage of the polymer (A) and generation of an unpleasant odor can be solved. In other words, when attempting to exceed 90% and approach 100%, an excessive amount of fluorinating agent is usually required in the manufacturing process. Therefore, components derived from the raw material fluorinating agent tend to remain in the polymer (A), which results in problems of yellow coloration and loss of transparency during storage of the polymer (A) and generation of an unpleasant odor. However, by setting the molar ratio at 60-90%, it has been possible to suppress the increase in viscosity and to achieve storage stability issues such as coloration and generation of an unpleasant odor during storage.

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

In the present invention, the amount of the fluorinating agent is reduced to partially fluorinate the silicon groups of the reactive silicon group-containing polyoxyalkylene polymer having reactive groups other than fluorine. To solve the above problem, the amount of the fluorinating agent is adjusted so that the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer is 60 to 90%. This makes it possible to suppress yellow coloration, unpleasant odor, and viscosity increase that occur when polymer (A) is stored alone. Furthermore, the molar ratio of Si-F bonds is preferably 70 to 85%.
That is, the present invention includes a method for producing a silicon group-containing polyoxyalkylene polymer (A) containing Si-F bonds, which comprises converting reactive groups of the reactive silicon group-containing polyoxyalkylene polymer to fluorine atoms with a fluorinating agent so that the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer is 60 to 90%. Furthermore, the molar ratio of Si-F bonds is preferably 70 to 85%.

When a polyoxyalkylene polymer containing dimethoxymethylsilyl groups is used as the raw polymer and the silicon groups in the raw polymer are converted to silicon groups containing Si-F bonds, the fluorination rate can be accurately determined by ^1H -NMR. Specifically, when the methoxy groups on silicon are converted to fluoro groups, the peak of the methyl groups on silicon shifts, and the molar ratios of difluoromethylsilyl groups, monofluoromethoxymethylsilyl groups, and dimethoxymethylsilyl groups in the polymer (A) can be obtained, and the fluorination rate can be calculated.

In the present invention, "in the entire polymer" in "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 entire polymer is 60 to 90%" refers to the entire polymer obtained by partially fluorinating the raw material polymer with a fluorinating agent, which may include completely fluorinated polymers and non-fluorinated polymers, and refers to the fluorination rate of the entire polymer.

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

The resulting silicon-containing polyoxyalkylene polymer (A) containing Si-F bonds may be linear or branched, and its number average molecular weight is preferably 3,000 to 30,000 as calculated in terms of polystyrene by GPC. If the number average molecular weight is less than 3,000, the elongation properties of the cured product tend to be poor, and if it exceeds 30,000, the viscosity becomes high, which tends to be poor in terms of workability.

The molecular weight distribution of the silicon-containing polyoxyalkylene polymer (A) containing Si-F bonds is preferably 1.6 or less, more preferably 1.4 or less, and even more preferably 1.3 or less. From the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, a molecular weight distribution of 1.2 or less is preferable. The molecular weight distribution can be determined from the number average molecular weight and 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 can be mixed with a reactive silicon group-containing polymer (B) having no Si-F bond to obtain a curable composition having fast curing properties.

<Reactive Silicon Group-Containing Polymer (B) Having No Si-F Bond>
The reactive silicon group-containing polymer (B) having no Si-F bond may be linear or branched, and its number average molecular weight, calculated as polystyrene by GPC, is preferably about 3,000 to 100,000, 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, the elongation properties of the cured product tend to be disadvantageous, while if it exceeds 100,000, the viscosity becomes high, which tends to be disadvantageous in terms of workability.

The molecular weight distribution of the reactive silicon group-containing polymer (B) that does not have a Si-F bond is preferably 1.6 or less, more preferably 1.4 or less, and even more preferably 1.3 or less. From the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, a molecular weight distribution of 1.2 or less is preferable. The molecular weight distribution can be determined from the number average molecular weight and weight average molecular weight obtained by GPC.

(Reactive silicon group having no Si-F bond)
The reactive silicon group having no Si—F bond contained in the polymer (B) is preferably a group represented by the general formula (3):
-SiR43 ^- _dYd ( ₃ )
(wherein each R ⁴ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an organosiloxy group represented by R ⁵ ₃ SiO- (each R ⁵ independently represents a hydrocarbon group having 1 to 20 carbon atoms), each Y independently represents a reactive group other than fluorine, and d is 1, 2, or 3).

The reactive group not having a Si-F bond in polymer (B) is not particularly limited and may be any reactive group known in the art. Specific examples include hydroxyl groups, halogen atoms other than fluorine, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, and alkoxy groups are particularly preferred from the viewpoint of mild hydrolysis and ease of handling.

When two or more reactive groups are bonded to a reactive silicon group, they may be the same or different.

Specific examples of ^R4 include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and _{triorganosiloxy groups represented by R53SiO-} ⁱⁿ which ^R5 is a methyl group, a phenyl group, etc. Of these, a methyl group is particularly preferred.

More specific examples of reactive silicon groups not having Si-F bonds in polymer (B) include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, methoxydimethylsilyl, ethoxydimethylsilyl, (methoxymethyl)dimethoxysilyl, and (chloromethyl)dimethoxysilyl groups. Trimethoxysilyl, triethoxysilyl, and dimethoxymethylsilyl groups are more preferred because they have high activity and good curing properties, and trimethoxysilyl and (methoxymethyl)dimethoxysilyl groups are particularly preferred. In addition, dimethoxymethylsilyl groups are particularly preferred from the standpoint of storage stability. Triethoxysilyl groups are particularly preferred because the alcohol produced by the hydrolysis reaction of the reactive silicon groups is ethanol, which makes them safer.

Polymers having reactive silicon groups, which have three reactive groups on the silicon atom, are also preferred because they tend to provide curable compositions with high curability and good recovery, durability, and creep resistance.

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, more preferably 0.7 to 5.0, and even more preferably 1.0 to 4.0. Furthermore, it is also possible to use a polymer (B) having an average of more than one reactive silicon group per terminal.

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

Specific examples of the main chain skeleton of polymer (B) include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, copolymers of isoprene or butadiene and acrylonitrile and/or styrene, etc., copolymers of polybutadiene, isoprene or butadiene and acrylonitrile and styrene, etc., and hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones; ethyl (meth)acrylate, butyl (meth)acrylate, etc. Examples of the polyamide polymer include (meth)acrylic acid ester polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, and styrene; vinyl polymers obtained by radical polymerization of monomers such as (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned polymers; polysulfide polymers; polyamide 6 obtained by ring-opening polymerization of ε-caprolactam, polyamide 6.6 obtained by condensation polymerization of hexamethylenediamine and adipic acid, polyamide 6.10 obtained by condensation polymerization of hexamethylenediamine and sebacic acid, polyamide 11 obtained by condensation polymerization of ε-aminoundecanoic acid, polyamide 12 obtained by ring-opening polymerization of ε-aminolaurolactam, and copolymerized polyamides having two or more components among the above-mentioned polyamides; organic polymers such as polycarbonate polymers and diallylphthalate polymers produced by condensation polymerization of bisphenol A and carbonyl chloride. Polysiloxane polymers such as polydiorganosiloxane can also be used. Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, (meth)acrylic acid ester polymers, and polysiloxane polymers are more preferred because they have a relatively low glass transition temperature and the cured product obtained when used as a curable composition has excellent cold resistance, polyoxyalkylene polymers and (meth)acrylic acid ester polymers are even more preferred, and polyoxyalkylene polymers are most preferred.

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

Methods for producing the reactive silicon-containing polyoxyalkylene polymer without Si-F bonds used as polymer (B) include (i) a method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst, and then converting the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene polymer to a carbon-carbon unsaturated group, and adding a silane compound by a hydrosilylation reaction; (ii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is reacted with a compound having both a group reactive with a hydroxyl group and a reactive silicon group; and (iii) a method in which a hydroxyl-terminated polyoxyalkylene polymer is reacted with an excess of a polyisocyanate compound to form a polymer having an isocyanate group at the end, and then reacting with a compound having both a group reactive with an isocyanate group and a reactive silicon group.

(Saturated Hydrocarbon Polymer)
The saturated hydrocarbon polymer is a polymer that does not substantially contain carbon-carbon unsaturated bonds other than aromatic rings, and the polymer constituting the skeleton thereof can be obtained by a method such as (1) polymerizing an olefin compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, etc., as a main monomer, or (2) homopolymerizing a diene compound, such as butadiene, isoprene, etc., or copolymerizing it with the above-mentioned olefin compound, followed by hydrogenation. Isobutylene polymers and hydrogenated polybutadiene polymers are preferred because functional groups can be easily introduced to the terminals, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased, and isobutylene polymers are particularly preferred.

Polymers whose main chain structure is saturated hydrocarbon-based have excellent heat resistance, weather resistance, durability, and moisture barrier properties.

The isobutylene polymer may be formed entirely of isobutylene units, or may be a copolymer with other monomers, but from the standpoint of rubber properties, it is preferable for it to contain 50% by weight or more of repeating units derived from isobutylene, more preferably 80% by weight or more, and particularly preferably 90 to 99% by weight.

Various polymerization methods have been reported for the synthesis of saturated hydrocarbon polymers, but in recent years, many so-called living polymerizations have been developed. Saturated hydrocarbon polymers, particularly isobutylene polymers, can be easily produced by using the inifer polymerization discovered by Kennedy et al. (J.P. Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, Vol. 15, p. 2843), which is known to be capable of polymerizing polymers with molecular weights of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and to introduce various functional groups to the molecular ends.

Methods for producing the reactive silicon group-containing saturated hydrocarbon polymer that does not have a Si-F bond, which is used as polymer (B), are described, for example, in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and JP-A-7-53882, but are not particularly limited thereto.

((Meth)acrylic acid ester polymer)
The (meth)acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (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, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and stearyl (meth)acrylate. Examples of (meth)acrylic acid monomers include glycidyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, γ-(methacryloyloxypropyl)dimethoxymethylsilane, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethylmethyl) (meth)acrylate), 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

In the (meth)acrylic acid ester polymer, the following vinyl monomers can also be copolymerized together with the (meth)acrylic acid ester monomer. Examples of the vinyl monomers include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butyl ... Examples of the monomer include maleimide monomers such as maleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

These may be used alone or in combination. In particular, polymers made of styrene monomers and (meth)acrylic acid monomers are preferred in terms of the physical properties of the product. More preferred are (meth)acrylic polymers made of acrylic acid ester monomers and methacrylic acid ester monomers, and particularly preferred are acrylic polymers made of acrylic acid ester monomers.

The synthesis method of the (meth)acrylic acid ester polymer is not particularly limited, and may be any known method. However, polymers obtained by normal free radical polymerization methods using azo compounds, peroxides, etc. as polymerization initiators have the problem that the molecular weight distribution is generally large, at 2 or more, and the viscosity is high. Therefore, in order to obtain a (meth)acrylic acid ester polymer having a molecular weight distribution of 1.6 or less, preferably 1.4 or less, a low viscosity, and a high proportion of crosslinkable functional groups at the molecular chain ends, it is preferable to use a living radical polymerization method.

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which (meth)acrylic acid ester monomers are polymerized using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts is even more preferable as a method for producing (meth)acrylic acid ester polymers having specific functional groups, since in addition to the characteristics of the above-mentioned "living radical polymerization method", the monomers have halogens at their ends, which are relatively advantageous for functional group conversion reactions, and there is a large degree of freedom in the design of initiators and catalysts. Examples of this atom transfer radical polymerization method include those described by Matyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.), 1995, Vol. 117, p. 5614.

As a method for producing the reactive silicon group-containing (meth)acrylic acid ester polymer without Si-F bonds used as polymer (B), for example, JP-B-3-14068, JP-B-4-55444, JP-A-6-211922, etc. disclose a method using a free radical polymerization method with a chain transfer agent. In addition, JP-A-9-272714, etc. disclose a method using an atom transfer radical polymerization method, but the method is not particularly limited to these.

(Polymer (B) having two or more kinds of main chain skeletons)
The polymer (B) having these various main chain skeletons may be used alone or in combination of two or more. Specifically, a polymer obtained by blending two or more selected from the group consisting of polyoxyalkylene polymers having reactive silicon groups without Si-F bonds, saturated hydrocarbon polymers having reactive silicon groups without Si-F bonds, and (meth)acrylic acid ester polymers having reactive silicon groups without Si-F bonds may also be used.

Methods for producing a polymer obtained by blending a polyoxyalkylene polymer containing a reactive silicon group having no Si-F bond with a (meth)acrylic acid ester polymer containing a reactive silicon group having no Si-F bond have been proposed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc., but are not particularly limited thereto. Preferred specific examples include a polymer having a reactive silicon group and having a molecular chain substantially represented by the following general formula (4):
—CH ₂ —C(R ⁷ )(COOR ⁸ )— (4)
(wherein ^R7 represents a hydrogen atom or a methyl group, and ^R8 represents an alkyl group having 1 to 8 carbon atoms), and a (meth)acrylic acid ester monomer unit having an alkyl group having 1 to 8 carbon atoms represented by the following general formula (5):
—CH ₂ —C(R ⁷ )(COOR ⁹ )— (5)
(wherein ^R7 is the same as defined above, and ^R9 is an alkyl group having 10 or more carbon atoms) is blended with a polyoxyalkylene polymer having a reactive silicon group not having a Si-F bond.

Examples of ^R8 in the general formula (4) include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, and a 2-ethylhexyl group. The alkyl group for ^R8 may be a single group or a mixture of two or more groups.

Examples of ^R9 in the general formula (5) include long-chain alkyl groups having 10 or more carbon atoms, usually 10 to 30, and preferably 10 to 20, such as lauryl, tridecyl, cetyl, stearyl, and behenyl. The alkyl group for ^R8 may be a single group or a mixture of two or more groups.

The molecular chain of the (meth)acrylic acid ester copolymer is substantially composed of monomer units of formula (4) and formula (5), where "substantially" means that the total of the monomer units of formula (4) and formula (5) present in the copolymer exceeds 50% by weight. The total of the monomer units of formula (4) and formula (5) is preferably 70% by weight or more.

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

Examples of monomer units other than those of formula (4) and formula (5) that may be contained in the copolymer include acrylic acids such as acrylic acid and methacrylic acid; monomers containing amide groups such as N-methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate; and monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ethers, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc.

Polymers obtained by blending a saturated hydrocarbon polymer containing a reactive silicon group that does not have a Si-F bond with a (meth)acrylic acid ester copolymer containing a reactive silicon group that does not have a Si-F bond have been proposed in JP-A-1-168764 and JP-A-2000-186176, but are not limited to these.

In addition, as a method for producing a polymer obtained by blending a (meth)acrylic acid ester copolymer containing a reactive silicon group that does not have a Si-F bond, a method of polymerizing a (meth)acrylic acid ester monomer in the presence of a polymer containing a reactive silicon group that does not have a Si-F bond can also 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, etc., but is not limited to these.

(Ratio of Polymer (A) to Polymer (B))
By mixing the polymer (A) with the polymer (B), a curable composition having fast curing properties can be obtained. The fast curing properties are determined by the ratio of the Si-F bonds present in the polymer (A) to all 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) per 100 parts by weight of the polymer (B), and more preferably 0.1 to 10 parts by weight. If the amount of the polymer (A) is less than 0.01 parts by weight, the effect of accelerating the curing rate may not be sufficient, and if the amount of the polymer (A) is more than 50 parts by weight, the strength of the cured product may be extremely reduced 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 plays a role in promoting the reaction of crosslinking by hydrolysis and condensation of the reactive silicon groups of the polymer (A) or polymer (B).

As the curing catalyst (C), various types of already known compounds such as organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, and inorganic acids can be used. However, from an environmental perspective, it is preferable to use non-organotin compounds as the curing catalyst. In particular, it is preferable to use amine compounds as the curing catalyst because they can rapidly cure the curable composition of the present invention despite being non-organotin catalysts.

The amine compounds that can be used as the curing catalyst (C) of the present invention also include nitrogen-containing cyclic compounds such as pyridine. Specific examples of amine compounds include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, and cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, and the like. aliphatic secondary amines such as triamylamine, trihexylamine, and trioctylamine; aliphatic tertiary amines such as triarylamine, triarylamine, and oleylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as aniline, laurylaniline, stearylaniline, and triphenylamine; pyridine, 2-aminopyridine, 2-(dimethylamino)pyridine, 4-(dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2-piperidinemethanol, 2-(2-piperidino)ethanol, piperidone, 1,2-dimethyl-1,4,5,6 -tetrahydropyrimidine, 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), 6-(dibutylamino)-1,8-diazabicyclo(5,4,0)undecene-7 (DBA-DBU), 1,5-diazabicyclo(4,3,0)nonene-5 (DBN), 1,4-diazabicyclo(2,2,2)octane (DABCO), heterocyclic compounds such as aziridine, and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, diethanolamine, dimethyl ... Examples of such amines include ethylenetriamine, triethylenetetramine, 2-(2-aminoethylamino)ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2-(1-piperazinyl)ethylamine, xylylenediamine, and 2,4,6-tris(dimethylaminomethyl)phenol; guanidines such as guanidine and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide, but are not limited to these.

Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, and DBN; guanidines such as guanidine and diphenylguanidine; and biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide are preferred because they exhibit high activity. In addition, aryl-substituted biguanides such as 1-o-tolylbiguanide and 1-phenylbiguanide are preferred because they exhibit high adhesiveness.

In addition, amine compounds exhibit basicity, but those with a conjugate acid pKa value of 11 or more are preferred because they have high catalytic activity. In particular, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN, etc. have a conjugate acid pKa value of 12 or more and are preferred because they exhibit high catalytic activity.

From the viewpoints 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. If the number of carbon atoms is smaller than this range, it tends to volatilize easily and have an increased odor. If the number of carbon atoms is larger than this range, it tends to become solid at room temperature, and compatibility with polymer (A) may be 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 hydrolyzable silicon group) and a substituted or unsubstituted amino group. Substituents of the substituted amino group include alkyl groups, aralkyl groups, and aryl groups. Examples of this hydrolyzable silicon group include groups represented by general formula (3) in which Y is a hydrolyzable group. Specifically, the groups already exemplified as hydrolyzable groups can be mentioned, but methoxy groups, ethoxy groups, etc. are preferred in terms 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)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl) Examples include aminopropyltrimethoxysilane, 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, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine.

As the aminosilane of the curing catalyst (C), from the viewpoint of curability, an aminosilane having an amino group ( _-NH2 ) is preferred, and from the viewpoint of availability, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-(2-aminoethyl)aminopropyltrimethoxysilane are preferred.

In addition, ketimine compounds that produce the above-mentioned amine compounds upon hydrolysis can also be used as the curing catalyst (C) of the present invention.

Specific examples of curing catalysts (C) other than amine compounds include carboxylic acids such as acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid; derivatives of the above-mentioned carboxylic acids (carboxylic acid anhydrides, esters, amides, nitriles, and acyl chlorides); tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, and calcium carboxylate. metal salts of carboxylates such as titanium, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate; titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis(acetylacetonate), bis(acetylacetonate)diisopropoxytitanium, and diisopropoxytitanium bis(ethylacetoacetate); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, and dibutyltin bis(ethylacetoacetate). dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(ethylacetonate) Examples of suitable organic tin compounds include organotin compounds such as aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), and diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis(acetylacetonate); various metal alkoxides such as tetrabutoxyhafnium; organic acid phosphate esters; organic sulfonic acids such as trifluoromethanesulfonic acid; and inorganic acids such as hydrochloric acid, phosphoric acid, and boronic acid. However, for the reasons described above, the amount of the organotin compound used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and even more preferably 0.05 parts by weight or less, relative to 100 parts by weight of the total amount of the polymer (A) and the polymer (B), and is particularly preferably not contained.

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

The amount of curing catalyst (C) used is preferably about 0.001 to 20 parts by weight, more preferably about 0.01 to 10 parts by weight, per 100 parts by weight of the total amount of polymer (A) and polymer (B). If the amount of curing catalyst (C) is below this range, it may be difficult to obtain a sufficient curing speed, and catalytic activity may decrease after storage. On the other hand, if the amount of curing catalyst (C) is above this range, the pot life may become too short, resulting in poor workability.

<Additives>
In addition to the polymer (A), the polymer (B), and the curing catalyst (C), the curable composition of the present invention may contain additives such as an adhesion imparting agent, a filler, a plasticizer, a tackifying resin, a solvent, a diluent, a physical property adjusting agent, a thixotropy imparting agent, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, an antioxidant, a light stabilizer, an ultraviolet absorber, an epoxy resin, a flame retardant, and other additives.

(Adhesion imparting agent)
The curable composition of the present invention can use a silane coupling agent as an adhesion promoter. The silane coupling agent referred to here is a compound having a hydrolyzable silicon group and other functional groups in the molecule, and when used on various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, and polycarbonate, it shows 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. It is also a compound that can function as a physical property adjuster, a dispersion improver for inorganic fillers, etc.

Examples of hydrolyzable silicon groups in silane coupling agents include groups represented by general formula (2) in which Y is a hydrolyzable group. Specific examples of hydrolyzable groups include those already listed as examples, but methoxy and ethoxy groups are preferred in terms of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, and more preferably 3 or more.

Examples of functional groups other than hydrolyzable silicon groups include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, etc. Among these, substituted or unsubstituted amino groups, epoxy groups, isocyanate groups, isocyanurates, etc. are preferred because of their high adhesiveness improving effect, and amino groups are particularly preferred.

Silane coupling agents having both a hydrolyzable silicon group and an amino group are generally called aminosilanes, but in the present invention, aminosilanes also function as curing catalysts. Therefore, in this specification, specific examples of aminosilanes are described in the explanation of the curing catalyst. Note that if it is desired to enhance the function as an adhesion promoter, aminosilane may be used in an amount greater than that required as a curing catalyst.

Specific examples of silane coupling agents other than aminosilanes include isocyanate silanes such as γ-isocyanate propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-isocyanate propyl methyl diethoxysilane, γ-isocyanate propyl methyl dimethoxysilane, (isocyanate methyl) trimethoxysilane, and (isocyanate methyl) dimethoxymethylsilane; ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine; mercaptosilanes such as γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, γ-mercaptopropyl methyl dimethoxysilane, γ-mercaptopropyl methyl diethoxysilane, and mercaptomethyl triethoxysilane; γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl tri Examples of the epoxy silanes include ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxy silanes include β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silanes include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropyltriethoxysilane; halogen-containing silanes include γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris(3-trimethoxysilylpropyl)isocyanurate. Also usable are reaction products of the above aminosilanes and epoxysilanes, reaction products of aminosilanes and isocyanatesilanes, and reaction products of aminosilanes and (meth)acryloyloxy group-containing silanes. Condensates obtained by partially condensing the above silanes can also be used. Furthermore, derivatives obtained by modifying these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

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

The amount of the silane coupling agent used in the present invention 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, per 100 parts by weight of polymer (A), or per 100 parts by weight of the total amount of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. If the blending amount is below this range, sufficient adhesion may not be obtained. If the blending amount is above this range, a practical curing speed may not be obtained, and the curing reaction may not proceed sufficiently.

In addition to the above-mentioned silane coupling agents, other adhesion promoters that can be used include, but are not limited to, epoxy resins, phenolic resins, sulfur, alkyl titanates, aromatic polyisocyanates, etc. The adhesion promoters 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 crosslinking agent and has the function of improving the recovery, 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 adhesion, water-resistant adhesion, and adhesion durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When silicate is used, the amount of silicate used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (A), or, in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

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

The partial hydrolysis condensation product of tetraalkoxysilane is more preferable because the effect of improving the recovery, durability, and creep resistance of the present invention is greater than that of tetraalkoxysilane.

The partial hydrolysis condensate of the tetraalkoxysilane may be, for example, a product obtained by adding water to a tetraalkoxysilane in a conventional manner to cause partial hydrolysis and condensation. In addition, a commercially available product may be used as the partial hydrolysis condensate of an organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

(filler)
A filler can be added to the composition of the present invention. Examples of the filler include reinforcing fillers such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, shirasu balloons, glass microballoons, organic microballoons of phenolic resins and vinylidene chloride resins, PVC powder, PMMA powder, and other resin powders; and fibrous fillers such as glass fibers and filaments. When a filler is used, the amount of the filler is preferably 1 to 250 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of the polymer (A), and more preferably 10 to 200 parts by weight, per 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.

As described in JP 2001-181532 A, the filler can be mixed uniformly with a dehydrating agent such as calcium oxide, sealed in an airtight bag, and left for an appropriate period of time to dehydrate and dry in advance. The use of this low moisture content filler can improve storage stability, particularly when used as a one-liquid composition.

In addition, when a highly transparent composition is to be obtained, as described in JP-A-11-302527, a polymer powder made from a polymer such as methyl methacrylate, or amorphous silica can be used as a filler. In addition, as described in JP-A-2000-38560, a highly transparent composition can be obtained by using hydrophobic silica, which is a silicon dioxide fine powder having hydrophobic groups bonded to its surface, as a filler. The surface of silicon dioxide fine powder is generally made of silanol groups (-SiOH), and hydrophobic silica is obtained by reacting this silanol group with an organic silicon halide, alcohols, or the like to generate (-SiO-hydrophobic groups). Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, or the like is reacted and bonded to the silanol groups present on the surface of silicon dioxide fine powder. Silicon dioxide fine powder whose surface is formed of silanol groups (-SiOH) is called hydrophilic silica fine powder.

If it is desired to obtain a hardened product with high strength by using these fillers, a filler selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, silicic acid hydrate, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide is preferred. A good result can be obtained by using 1 to 200 parts by weight per 100 parts by weight of polymer (A), or 100 parts by weight of the total of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. Also, if it is desired to obtain a hardened product with low strength and high breaking elongation, a filler selected from titanium oxide, calcium carbonate such as heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon is preferred. A good result can be obtained by using 5 to 200 parts by weight of a filler selected from titanium oxide, calcium carbonate such as heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon, or 100 parts by weight of the total of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. In general, the larger the specific surface area 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 types. When using calcium carbonate, it is desirable to use a combination of surface-treated fine calcium carbonate and calcium carbonate with 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 is preferably treated with a fatty acid or fatty acid salt. Furthermore, the particle size of the large calcium carbonate is preferably 1 μm or more, and non-surface-treated calcium carbonate can be used.

To improve the workability (sharpness, etc.) of the composition and to give the cured product a matte surface, it is preferable to add organic or inorganic balloons. These fillers can also be used for surface treatment, and may be used alone or in combination with two or more types. To improve workability (sharpness, etc.), the particle size of the balloons is preferably 0.1 mm or less. To give the cured product a matte surface, it is preferable to use a particle size of 5 to 300 μm.

The composition of the present invention is suitable for use in sizing boards, particularly ceramic sizing boards, and other joints in the exterior walls of houses, as adhesives for exterior wall tiles, and adhesives for exterior wall tiles that leave the adhesive in the joints. It is desirable that the design of the exterior wall and the design of the sealant harmonize. In particular, exterior walls that have a luxurious feel due to sputter painting and the inclusion of colored aggregates are being used. If the composition of the present invention contains a scaly or granular material with a diameter of 0.1 mm or more, preferably 0.1 to 5.0 mm, the cured product will harmonize with such a luxurious exterior wall, and since the composition has excellent chemical resistance, the appearance of the cured product will last for a long time. If a granular material is used, the surface will have a rough sand or sandstone texture, and if a scaly material is used, the surface will have an uneven texture due to the scaly shape.

The preferred diameter, amount, and materials of the scaly or granular substances 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 and pattern of the exterior wall. About 0.2 mm to 5.0 mm or 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 either premixed into the main sealing material and transported to the construction site as a sealant, or mixed into the main sealing material at the construction site when used.

The scale-like or granular substance is mixed in an amount of about 1 to 200 parts by weight per 100 parts by weight of the composition, such as the sealant composition or adhesive composition. The amount to be mixed is appropriately selected depending on the size of each scale-like or granular substance, the material of the exterior wall, the pattern, etc.

Scaly or granular substances that can be used include natural substances such as silica sand and mica, as well as inorganic substances such as synthetic rubber, synthetic resin, and alumina. In order to improve the design when filled into the joints, they are colored appropriately to match the material and pattern of the exterior wall.

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

For the same purpose, balloons (preferably with an average particle size of 0.1 mm or more) can be used to create a rough, sandy or sandstone-like surface, while also reducing weight. The preferred diameter, amount, and materials of the balloons are as follows, as described in JP-A-10-251618:

The balloon is hollow and made of spherical filler. The material of the balloon includes inorganic materials such as glass, silas, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran, but is not limited to these. Inorganic and organic materials can be combined, or laminated to form multiple layers. Inorganic or organic balloons, or combinations of these, can be used. The balloons used can be the same or a mixture of multiple types of balloons made of different materials. Furthermore, the balloons can be surface-treated or coated, or can be surface-treated with various surface treatment agents. For example, organic balloons can be coated with calcium carbonate, talc, titanium oxide, etc., or inorganic balloons can be surface-treated with a silane coupling agent.

To obtain a rough surface with a sandy or sandstone texture, the particle size of the balloons is preferably 0.1 mm or more. Balloons with a particle size of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm can also be used. Balloons with a particle size of less than 0.1 mm may only increase the viscosity of the composition even if a large amount is added, and may not provide a rough texture. The amount of balloons to be added can be easily determined depending on the desired degree of roughness of the sandy or sandstone texture. Usually, it is desirable to add balloons with a particle size of 0.1 mm or more in a ratio that results in a volume concentration in the range of 5 to 25 vol% in the composition. If the volume concentration of the balloons is less than 5 vol%, there will be no rough texture, and if it exceeds 25 vol%, the viscosity of the sealant or adhesive will increase, making it difficult to work with, and the modulus of the cured product will also increase, tending to impair the basic performance of the sealant or adhesive. A volume concentration that is particularly preferable for balancing with the basic performance of the sealant is 8 to 22 vol%.

When using balloons, it is possible to add an anti-slip agent as described in JP-A-2000-154368, or an amine compound to make the surface of the cured product uneven and matte as described in JP-A-2001-164237, particularly a primary and/or secondary amine with a melting point of 35°C or higher.

Specific examples of balloons are described in 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-10-251618, JP-A-2000-154368, JP-A-2001-164237, WO97/05201, and other publications.

Thermal expandable hollow microparticles described in JP-A-2004-51701 or JP-A-2004-66749 can also be used. Thermally expandable hollow microparticles are plastic spheres in which a low-boiling point compound such as a hydrocarbon having 1 to 5 carbon atoms is spherically wrapped in a polymeric shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer). By heating the adhesive portion using this composition, the gas pressure inside the shell of the thermally expandable hollow microparticle increases, and the polymeric shell material softens, dramatically expanding its volume and playing a role in peeling the adhesive interface. By adding thermally expandable hollow microparticles, an adhesive composition can be obtained that can be peeled off by simply heating when not needed without destroying the material, and can be peeled off by heating without using any organic solvents.

When the composition of the present invention contains sealant cured particles, the cured product can form unevenness on the surface, improving the design. The preferred diameter, amount, and material of the sealant cured particles are as follows, as described in JP 2001-115142 A. The diameter is preferably 0.1 mm to 1 mm, and more preferably about 0.2 to 0.5 mm. The amount is preferably 5 to 100% by weight in the curable composition, and more preferably 20 to 50% by weight. Materials include urethane resin, silicone, modified silicone, polysulfide rubber, etc., and are not limited as long as they are used in sealants, but modified silicone sealants are preferred.

(Plasticizer)
A plasticizer can be added to the composition of the present invention. The addition of a plasticizer can adjust the viscosity and slump of the curable composition, and the mechanical properties such as the tensile strength and elongation of the cured product obtained by curing the composition. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, bis(2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

Polymeric plasticizers can also be used. When polymeric plasticizers are used, the initial physical properties can be maintained for a long period of time compared to when low molecular weight plasticizers, which are plasticizers that do not contain polymer components in the molecule, are used. Furthermore, the drying properties (also called paintability) can be improved when an alkyd paint is applied to the cured product. Specific examples of polymer plasticizers 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 plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol having a molecular weight of 500 or more, or even 1000 or more, or derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, or the like; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene, but are not limited to these.

Among these polymer plasticizers, when polymer (A), polymer (A) and polymer (B) are contained, those compatible with polymer (A) and polymer (B) are preferred. From this point of view, polyethers and vinyl polymers are preferred. In addition, when polyethers are used as plasticizers, the surface curability and deep curability are improved, and curing delay after storage does not occur, so they are preferred, and polypropylene glycol is more preferred among them. In addition, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance and heat resistance. Among vinyl polymers, acrylic polymers and/or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. As a method for synthesizing this polymer, the living radical polymerization method is preferred because it has a narrow molecular weight distribution and can reduce viscosity, and the atom transfer radical polymerization method is more preferred. In addition, it is preferable to use a polymer obtained by the so-called SGO process, which is obtained by continuous bulk polymerization of acrylic acid alkyl ester monomers at high temperature and high pressure as described in JP-A-2001-207157.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, even more preferably 1,000 to 8,000, and particularly preferably 1,000 to 5,000. Most preferably 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat or rain, making it impossible to maintain the initial physical properties over a long period of time, causing contamination due to dust adhesion, and not improving alkyd paintability. If the molecular weight is too high, the viscosity will increase and workability will deteriorate. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, and is preferably less than 1.80. It is more preferably 1.70 or less, even more preferably 1.60 or less, even more preferably 1.50 or less, particularly preferably 1.40 or less, and most preferably 1.30 or less.

The number average molecular weight is measured by end group analysis for polyether polymers, and by GPC for other polymers. The molecular weight distribution (Mw/Mn) is measured by GPC (polystyrene equivalent).

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 acts as a reactive plasticizer and can prevent the migration of the plasticizer from the cured product. When it has a reactive silicon group, it is preferable that the number of reactive silicon groups is 1 or less on average per molecule, and more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight is preferably lower than that of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. Otherwise, the plasticizing effect may not be obtained.

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

The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of polymer (A) or, when polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B). If the amount is less than 5 parts by weight, the effect as a plasticizer will not be manifested, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

(Tackifying Resin)
A tackifier can be added to the composition of the present invention. The tackifier resin is not particularly limited, but can be any resin that is commonly used regardless of whether it is solid or liquid at room temperature. Specific examples include styrene block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (e.g., cashew oil modified phenolic resins, tall oil modified phenolic resins, etc.), terpene phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene resins, DCPD resins, and petroleum resins. These may be used alone or in combination of two or more. Examples of styrene-based block copolymers and hydrogenated products thereof include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylenebutylene-styrene block copolymers (SEBS), styrene-ethylenepropylene-styrene block copolymers (SEPS), styrene-isobutylene-styrene block copolymers (SIBS), etc. The above tackifying resins may be used alone or in combination of two or more kinds.

The tackifying resin is preferably used in an amount of 5 to 1,000 parts by weight, more preferably 10 to 100 parts by weight, per 100 parts by weight of polymer (A), or, in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

(Solvent or Diluent)
A solvent or diluent can be added to the composition 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, etc. can be used. When using a solvent or diluent, 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, in view of the problem of air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more kinds.

(Physical property adjuster)
The curable composition of the present invention may contain a physical property adjuster for adjusting the tensile properties of the resulting cured product as necessary. The physical property adjuster is not particularly limited, but examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, and other alkoxysilanes having unsaturated groups; silicone varnishes; and polysiloxanes. By using the physical property adjuster, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be reduced to provide a breaking elongation. The physical property adjuster may be used alone or in combination of two or more kinds.

In particular, compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis have the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. In particular, compounds that generate trimethylsilanol are preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521. In addition, compounds that generate silicon compounds that are derivatives of alkyl alcohols such as hexanol, octanol, and decanol and generate R ₃ SiOH such as trimethylsilanol by hydrolysis, and compounds that generate silicon compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol and generate R ₃ SiOH such as trimethylsilanol by hydrolysis, as described in JP-A-11-241029, can be mentioned.

Further examples include compounds which are derivatives of oxypropylene polymers and which produce silicon compounds which produce _RSiOH such as trimethylsilanol upon hydrolysis, as described in JP-A-7-258534.Furthermore, polymers having crosslinkable hydrolyzable silicon-containing groups and silicon-containing groups which can become monosilanol-containing compounds upon hydrolysis, as described in JP-A-6-279693, can also be used.

The physical property adjusting agent can be used in an amount of preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (A), or, in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

(Thixotropy imparting agent)
The curable composition of the present invention may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability, if necessary. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. In addition, by using 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, a composition having high thixotropy and good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more kinds. The thixotropic agent may be used in an amount of preferably 0.1 to 20 parts by weight per 100 parts by weight of polymer (A), or in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

(Epoxy group-containing compound)
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 improve the restorability of the cured product. Examples of compounds 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. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. Among these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of polymer (A), or in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

(Photocurable substances)
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, improving the stickiness and weather resistance of the cured product. A photocurable substance is a substance whose molecular structure undergoes a chemical change in a fairly short time due to the action of light, resulting in a physical change such as curing. Many compounds of this type are known, such as organic monomers, oligomers, resins, or compositions containing them, and any commercially available one can be used. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, such as propylene (or butylene, ethylene) glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and the like, or oligoesters having a molecular weight of 10,000 or less. Specific examples include special acrylates (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, and Aronix M-245; (trifunctional) Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, and Aronix M-325, and (multifunctional) Aronix M-400, but compounds containing acrylic functional groups are particularly preferred, and compounds containing an average of three or more of the same functional groups per molecule are also preferred. (All of the above Aronixes are products of Toagosei Chemical Industry Co., Ltd.)

Examples of polyvinyl cinnamates include photosensitive resins with cinnamoyl groups as photosensitive groups, such as polyvinyl alcohol esterified with cinnamic acid, as well as many other polyvinyl cinnamate derivatives. Azido resins are known as photosensitive resins with azide groups as photosensitive groups, and are usually rubber photosensitive solutions to which diazide compounds have been added as photosensitizers, as well as detailed examples in "Photosensitive Resins" (published March 17, 1972, by the Printing Society Publishing Division, pp. 93-106-117-). These can be used alone or in mixtures, with the addition of a sensitizer as necessary. 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 preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (A), or, when polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B). If the amount of photocurable substance used is less than 0.1 parts by weight, it may not be effective in improving weather resistance, and if it is more than 20 parts by weight, the cured product will be too hard and prone to cracking.

(Oxygen-curable substances)
The composition of the present invention can contain an oxygen-curable substance. Examples of the oxygen-curable substance include unsaturated compounds that can react with oxygen in the air, and when reacted with oxygen in the air, form a cured film near the surface of the cured product, thereby preventing the surface from becoming sticky and preventing the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen curing substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and liquid copolymers such as NBR and SBR obtained by copolymerizing these diene compounds with monomers such as acrylonitrile and styrene having copolymerizability so that the diene compounds are the main component, and various modified products thereof (malein modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Among these, tung oil and liquid diene polymers are particularly preferred. In addition, the effect may be enhanced by using a catalyst or metal dryer that promotes the oxidative curing reaction in combination. Examples of these catalysts and metal driers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, and amine compounds. The amount of oxygen curing material used is preferably in the range of 0.1 to 20 parts by weight per 100 parts by weight of polymer (A), and more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total amount of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. If the amount used is less than 0.1 part by weight, the improvement of contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, it is preferable to use the oxygen curing material in combination with a photocuring material.

(Antioxidant)
An antioxidant (antiaging agent) can be used in the composition of the present invention. The use of an antioxidant can improve the heat resistance of the cured product. Examples of antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based, with hindered phenol-based being particularly preferred. Similarly, hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Chiba Specialty Chemicals Co., Ltd.), MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN LS-770, TINUVIN LS-765, TINUVIN LS-292, TINUVIN LS-2626, TINUVIN LS-1114, TINUVIN LS-744 (all manufactured by Sankyo Co., Ltd.) can also be used. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably within a range of 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A), or per 100 parts by weight of the total amount of the polymer (A) and the polymer (B) in the case where the polymer (A) and the polymer (B) are contained.

(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 light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred. The amount of light stabilizer used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of polymer (A), and more preferably 0.2 to 5 parts by weight per 100 parts by weight of the total amount of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. Specific examples of light stabilizers are also described in JP-A-9-194731.

When a photocurable substance is used in the composition of the present invention, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine-based light stabilizer as the hindered amine-based light stabilizer in order to improve the storage stability of the composition, as described in JP-A-5-70531. Examples of tertiary amine-containing hindered amine-based light stabilizers include light stabilizers such as TINUVIN 622LD, TINUVIN 144, and CHIMASSORB119FL (all manufactured by Chiba Specialty Chemicals Co., Ltd.); MARK LA-57, LA-62, LA-67, and LA-63 (all manufactured by Asahi Denka Kogyo Co., Ltd.); and TINUVIN LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all manufactured by Sankyo Co., Ltd.).

(Ultraviolet absorber)
The composition of the present invention may contain an ultraviolet absorber. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred. The amount of ultraviolet absorber used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of polymer (A), and more preferably 0.2 to 5 parts by weight per 100 parts by weight of the total amount of polymer (A) and polymer (B) when polymer (A) and polymer (B) are contained. 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)
An epoxy resin can be added to the composition of the present invention. The composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Examples of epoxy resins include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, and glycidyl ether of tetrabromobisphenol A, novolac type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, and epoxidized products of unsaturated polymers such as petroleum resins, but are not limited thereto. Generally used epoxy resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. When these epoxy resins and polymer (A) or polymer (A) and polymer (B) are contained, the ratio of the total amount of polymer (A) and polymer (B) used is preferably ((A) or (A) + (B))/epoxy resin = 100/1 to 1/100 by weight. If 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 epoxy resin cured product, and if the ratio of ((A) or (A) + (B))/epoxy resin is more than 100/1, the strength of the organic polymer cured product tends to be insufficient. The preferred use ratio cannot be generally determined because it varies depending on the application of the curable resin composition, but for example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of an epoxy resin cured product, it is preferable to use 1 to 100 parts by weight of polymer (A) or, when polymer (A) and polymer (B) are contained, the total amount of polymer (A) and polymer (B) is preferably 5 to 100 parts by weight per 100 parts by weight of epoxy resin. On the other hand, when improving the strength of a cured product of the polymer (A) component, it is preferable to use 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of epoxy resin per 100 parts by weight of polymer (A) or, when polymer (A) and polymer (B) are contained, the total amount of polymer (A) and polymer (B) is 100 parts by weight.

When an epoxy resin is added, it goes without saying that a curing agent for curing the epoxy resin can be used in combination with the composition of the present invention. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used. Specific examples of the compounds include, but are not limited to, primary and secondary amines such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, and amine-terminated polyethers; tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, and chlorenic anhydride; alcohols; phenols; carboxylic acids; and diketone complex compounds of aluminum or zirconium. In addition, the curing agent may be used alone or in combination of two or more types.

When using an epoxy resin hardener, the amount used is preferably 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

Ketimines can be used as curing agents for epoxy resins. Ketimines are stable in the absence of moisture, but are decomposed into primary amines and ketones by moisture, and the resulting primary amines become room-temperature curing agents for epoxy resins. By using ketimines, it is possible to obtain one-liquid compositions. Such ketimines can be obtained by the condensation reaction of an amine compound with a carbonyl compound.

Known amine compounds and carbonyl compounds may be used to synthesize ketimines. Examples of amine compounds that can be used include diamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, and p,p'-biphenylenediamine; polyamines such as 1,2,3-triaminopropane, triaminobenzene, tris(2-aminoethyl)amine, and tetrakis(aminomethyl)methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; polyoxyalkylene polyamines; and aminosilanes such as γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. In addition, examples of carbonyl compounds that can be used include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, and diisobutyl ketone; and β-dicarbonyl compounds such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methyl ethyl malonate, and dibenzoylmethane.

When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ethers such as butyl glycidyl ether and allyl glycidyl ether; glycidyl esters, etc. These ketimines may be used alone or in combination of two or more kinds. They can be used in an amount of 1 to 100 parts by weight per 100 parts by weight of epoxy resin, and the amount used can be set appropriately depending on the type of epoxy resin and ketimine.

(Flame retardants)
The curable composition of the present invention may contain a phosphorus-based plasticizer such as ammonium polyphosphate or tricresyl phosphate, or a flame retardant such as aluminum hydroxide, magnesium hydroxide, or thermally expandable graphite. The flame retardants may be used alone or in combination of two or more.

The flame retardant is preferably used in an amount of 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, per 100 parts by weight of polymer (A), or, in the case where polymer (A) and polymer (B) are contained, per 100 parts by weight of the total amount of polymer (A) and polymer (B).

(Other additives)
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, termite inhibitors, and fungicides. These various additives may be used alone or in combination of two or more. Specific examples of the additives other than those listed in this specification are described, for example, in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2001-72854.

<Preparation of Curable Composition>
The curable composition of the present invention can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed state, and then cured by moisture in the air after application, or as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with the polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

When the curable composition is a one-component type, all the ingredients are mixed in advance, so it is preferable to dehydrate the ingredients containing water before use, or to dehydrate them by reducing pressure during mixing. When the curable composition is a two-component type, there is no need to mix a curing catalyst into the base agent containing a polymer having a reactive silicon group, so there is little risk of gelation even if the ingredients contain a small amount of water, but it is preferable to dehydrate them when long-term storage stability is required. As for the dehydration and drying method, the heat drying method is suitable for solid substances such as powders, and the reduced pressure dehydration method or dehydration methods using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. are suitable for liquid substances. In addition, a small amount of an isocyanate compound may be mixed to react the isocyanate group with water to dehydrate. In addition, an oxazolidine compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be mixed and reacted with water to dehydrate. In addition to this dehydration and drying method, storage stability can be further improved by adding lower alcohols such as methanol and ethanol; or alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

The amount of the dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymer (A), or per 100 parts by weight of the total amount of polymer (A) and polymer (B) if polymer (A) and polymer (B) are contained.

There are no particular limitations on the method for preparing the curable composition of the present invention, and any conventional method can be used, such as blending the above-mentioned components and kneading them at room temperature or under heat using a mixer, roll, kneader, or the like, or dissolving the components using a small amount of a suitable solvent and mixing them.

When the curable composition of the present invention is exposed to the atmosphere, it forms a three-dimensional network due to the action of moisture and hardens into a solid with rubber-like elasticity.

<Applications>
The curable composition of the present invention can be used as a pressure sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold release agent, an anti-vibration material, a vibration damping material, a soundproofing material, a foaming material, a paint, a spray material, etc. The cured product obtained by curing the curable composition of the present invention has excellent flexibility and adhesiveness, and therefore, among these, it is more preferably used as a sealing material or an adhesive.

It can also be used in a variety of applications, such as electrical and electronic component materials, such as solar cell backside sealing materials, electrical insulating materials, such as insulating coating materials for electric wires and cables, elastic adhesives, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealants, food packaging materials, joint sealants for exterior materials such as sizing boards, coating materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust and waterproof sealants for wired glass and laminated glass end faces (cut parts), and liquid sealants used in automobile parts, electrical parts, various machine parts, etc. Furthermore, it can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, and can also be used as various types of sealing compositions and adhesive compositions. The curable composition of the present invention can also be used as an adhesive for interior panels, exterior panels, tile adhesives, stone veneer adhesives, ceiling finishing adhesives, floor finishing adhesives, wall finishing adhesives, vehicle panel adhesives, adhesives for assembling electrical, electronic, and precision equipment, direct glazing sealants, double-glazing sealants, SSG construction sealants, or working joint sealants for buildings.

Next, the present invention will be specifically explained using examples and comparative examples, but the present invention is not limited to these.

The fluorination rate in the examples was calculated from the results of ¹ H-NMR measurement using AVANCEIIIHD500 manufactured by Bruker, which was dissolved in deuterated chloroform. When a dimethoxymethylsilyl group-terminated polyoxyalkylene polymer is fluorinated, the fluorination rate can be accurately determined by ¹ H-NMR. Specifically, when a methoxy group on silicon is modified to a fluoro group, the peak of the methyl group on silicon shifts, and the molar ratio of the difluoromethylsilyl group, monofluoromethoxymethylsilyl group, and dimethoxymethylsilyl group in the polymer (A) can be calculated, and therefore the fluorination rate can be calculated.

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

The appearance in the examples was measured by visually comparing the transmitted color of the sample with the Gardner color standard solution prepared using potassium hexachloroplatinate (IV), iron (III) chloride, cobalt (II) chloride, and hydrochloric acid, based on the Gardner color scale test method (JIS K 0071-2). In Table 1, the sample is described as colorless if it was colorless or had slight coloring less than that of the G-1 standard solution, and as colored if it had clear coloring equal to or greater than that of the G-1 standard solution.

(Synthesis Example 1)
Polyoxypropylene glycol having a number average molecular weight of about 4500 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 14,300 and a molecular weight distribution Mw/Mn=1.21, which has hydroxyl groups at both ends. 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After distilling off the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation, and the metal salt in the polymer was removed by devolatilizing the hexane from the obtained hexane solution under reduced pressure. As a result, polyoxypropylene having allyl groups at the ends was obtained. 50 ppm of platinum divinyldisiloxane complex solution (3 wt% isopropanol solution calculated as platinum) was added to 100 parts by weight of this polymer, and 1.7 parts by weight of dimethoxymethylsilane was slowly added dropwise while 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 and dimethoxymethylsilyl groups at the terminals. It was found that polymer (B-1) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.5 dimethoxymethylsilyl groups per molecule.

Example 1
5 parts of methanol was added to 100 parts by weight of dimethoxymethylsilyl-terminated polyoxypropylene polymer (B-1) and stirred. 0.94 parts by weight of _BF3 -methanol complex ( _BF3.2MeOH ) was slowly dropped according to the recipe in the table below under a nitrogen gas flow, and the reaction solution was allowed to react for 3 hours at an internal temperature of 38°C. Volatilization was performed under reduced pressure so that the internal pressure was 5 Torr or less, and methanol and _BF3- derived components were removed until the amount of remaining methanol was 3000 ppm or less by GC measurement, to obtain a silicon-containing polyoxypropylene polymer (A-1) containing Si-F bonds and having a number average molecular weight of 15,000. ^1H -NMR measurement confirmed that 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 the fluorination rate in the following text and in the table) was 67%. 10 mL of polymer (A-1) was placed in a 20 mL transparent glass vial, nitrogen was sealed inside, the vial was capped, and the vial was stored at 80° C. for one week, after which the changes in viscosity and appearance were examined. The results are shown in Table 1 below.

Example 2
A silicon-containing polyoxypropylene polymer ( _A -2) containing Si-F bonds with a fluorination rate of 71% and a number average molecular weight of 15,000 was obtained in the same manner as in Example 1, except that the amount of _BF3 methanol complex (BF3.2MeOH) used was 0.99 parts by weight. As in Example 1, the polymer (A-2) was stored at 80°C and examined for changes in viscosity and appearance, and for the presence or absence of an unpleasant odor. The results are shown in Table 1 below.

Example 3
A silicon-containing polyoxypropylene polymer (A- ₃ ) containing Si-F bonds and having a number average molecular weight of 15,000 and a fluorination rate of 86% was obtained in the same manner as in Example 1, except that the amount of _BF3 -methanol complex (BF3.2MeOH) used was 1.16 parts by weight. As in Example 1, the polymer (A-3) was stored at 80°C and examined for changes in viscosity and appearance, and for the presence or absence of an unpleasant odor. The results are shown in Table 1 below.

Example 4
A silicon-containing polyoxypropylene polymer (A- ₄ ) containing Si-F bonds with a number average molecular weight of 15,000 and a fluorination rate of 90% was obtained in the same manner as in Example 1, except that the amount of _BF3 methanol complex (BF3.2MeOH) used was 1.26 parts by weight. As in Example 1, the polymer (A-4) was stored at 80°C and examined for changes in viscosity and appearance, and for the presence or absence of an unpleasant odor. The results are shown in Table 1 below.

(Comparative Example 1)
A silicon-containing polyoxypropylene polymer ( _A -5) containing Si-F bonds with a number average molecular weight of 15,000 and a fluorination rate of 50% was obtained in the same manner as in Example 1, except that the amount of _BF3 methanol complex (BF3.2MeOH) used was 0.70 parts by weight. As in Example 1, the polymer (A-5) was stored at 80°C and examined for changes in viscosity and appearance, and for the presence or absence of an unpleasant odor. The results are shown in Table 1 below.

(Comparative Example 2)
A silicon-containing polyoxypropylene polymer ( _A -6) having a number average molecular weight of 15,000 and containing Si-F bonds with a fluorination rate of >99% was obtained in the same manner as in Example 1, except that the amount of _BF3 methanol complex (BF3.2MeOH) used was 1.54 parts by weight. As in Example 1, the polymer (A-6) was stored at 80°C and examined for changes in viscosity and appearance, and for the presence or absence of an unpleasant odor. The results are shown in Table 1 below.

(Synthesis Example 2)
22.0 parts by weight of isobutanol was placed in a four-neck flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 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 0.35 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 17.5 parts by weight of isobutanol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 1.5 hours, and the isobutanol was removed from the resulting polyacrylic polymer in the isobutanol solution by heating under reduced pressure to obtain a poly(meth)acrylic acid ester polymer (B-2) having an average of 0.9 dimethoxymethylsilyl groups per molecule, a number average molecular weight of 4,300, and a weight average molecular weight of 8,300.

(Reference Example 1)
5 parts of methanol was added to 100 parts by weight of the dimethoxysilyl group-terminated acrylic acid ester polymer (B-2) and stirred. 2.27 parts by weight of _BF3 -methanol complex ( _BF3.2MeOH ) was slowly dropped according to the recipe in the table below under a nitrogen gas flow, and the reaction solution was allowed to react for 3 hours at an internal temperature of 38°C. The internal pressure was reduced to 5 Torr or less and devolatilized, and methanol and _BF3 -derived components were removed until the amount of remaining methanol was 3000 ppm or less by GC measurement, to obtain a silicon-containing acrylic acid ester polymer (A-7) containing Si-F bonds and having a number average molecular weight of 4,700. ^1H -NMR measurement confirmed the disappearance of peaks derived from the raw materials. In other words, it was confirmed that the fluorination rate was >99%. As in Example 1, (A-7) was stored at 80°C and examined for changes in viscosity and appearance and the presence or absence of unpleasant odor, and no coloring, thickening, or unpleasant odor was observed.

In Examples 1-4, in which the fluorination rate was 60-90%, no obvious coloring was observed in the appearance after one week at 80° C., there was no unpleasant odor, and the viscosity did not exceed 50 Pa·s. In Comparative Example 1, in which the fluorination rate was low, a large increase in viscosity occurred after storage, exceeding 50 Pa·s. In Comparative Example 2, in which the fluorination rate was high, coloring was observed in the appearance both immediately after synthesis and after storage, and an unpleasant odor was generated.
In Reference Example 1 using an acrylic acid ester polymer, there were no problems with coloration or unpleasant odor, despite the fluorination rate being >99%.

Claims (12)

A silicon-containing polyoxyalkylene polymer (A) containing Si-F bonds, in which 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 entire polymer is 60 to 90%. The silicon-containing polyoxyalkylene polymer (A) according to claim 1, wherein the molar ratio of Si-F bonds to the total number of moles of Si-F bonds and Si-Z bonds in the entire polymer is 70 to 85%. The silicon group containing a Si—F bond is represented by the following general formula (1):
-SiF _a R ¹ _b Z _c (1)
(wherein R ¹ 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an organosiloxy group represented by R ² ₃ SiO- (wherein R ² 's each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms); each Z is independently a reactive group other than fluorine; a is 1, 2 or 3; b is 0, 1 or 2; c is 0, 1 or 2; and a+b+c is 3. When b or c is 2, the two R ¹ 's or the two Z's may be the same or different.) A silicon-containing polyoxyalkylene polymer (A) containing Si-F bonds according to any one of claims 1 to 3, having a number average molecular weight of 3,000 to 30,000. The silicon-containing polyoxyalkylene polymer (A) having a Si-F bond according to any one of claims 1 to 4, wherein Z is an alkoxy group. A curable composition comprising a silicon group-containing polyoxyalkylene polymer (A) containing a Si-F bond according to any one of claims 1 to 5, and a reactive silicon group-containing polymer (B) having no Si-F bond, in which the polymer (A) is present in an amount of 0.01 to 50 parts by weight per 100 parts by weight of the polymer (B). The curable composition according to claim 6, further comprising a curing catalyst (C). The curable composition according to claim 7, wherein the curing catalyst (C) is an amine compound. A sealant made using the curable composition according to any one of claims 6 to 8. An adhesive made 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-containing polyoxyalkylene polymer (A) containing Si-F bonds, in which reactive groups of the reactive silicon-containing polyoxyalkylene polymer are converted to fluorine atoms using a fluorinating agent, so that the molar ratio of Si-F bonds to the total molar number of Si-F bonds and Si-Z bonds (Z is a reactive group other than fluorine) in the entire polymer is 60 to 90%.