JP6096320B2 - Curable composition - Google Patents

Description

  The present invention relates to a reactive silicon group-containing polymer having an average of more than 1.0 reactive silicon groups at the terminals, and a reactive silicon group-containing polymer having 1.0 or less reactive silicon groups at the terminals. The present invention relates to a curable composition comprising

  Reactive silicon group-containing polymers are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealing materials, coating materials, paints, and adhesives, and are used in a wide range of fields. (Patent Document 1).

  As a polymer component of such a reactive silicon group-containing polymer, the main chain skeleton has various polymers such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester copolymer. In particular, polyoxyalkylene polymers have a relatively low viscosity at room temperature and are easy to handle, and a cured product obtained after the reaction also exhibits good elasticity.

  The polyoxyalkylene polymer is generally polymerized by ring-opening polymerization of an epoxy compound. Polymerization method using an alkali catalyst such as KOH, polymerization method using a transition metal compound-porphyrin complex catalyst, composite metal cyanide It can be obtained using a polymerization method using a complex catalyst, a polymerization method using a catalyst comprising a polyphosphazene salt, a polymerization method using a catalyst comprising a phosphazene compound, and the like.

  The obtained polyoxyalkylene polymer has a hydroxyl group at the terminal, and after converting the hydroxyl group to a carbon-carbon unsaturated group, a hydrosilylation reaction between the carbon-carbon unsaturated group and the silane compound is performed. As a result, a reactive silicon group-containing polyoxyalkylene polymer can be obtained (Patent Document 2). In addition, it is known that when a reactive silicon group having Si bonded with an electron-withdrawing group is used as the reactive silicon group, the reaction rate is improved (Patent Document 3). The reactive silicon group-containing polyoxyalkylene polymer obtained by this method has an average of 1.0 or less reactive silicon groups at one end.

  On the other hand, a method for synthesizing a polyoxyalkylene polymer having a plurality of reactive silicon groups at one terminal is also known (Patent Documents 4 and 5). However, these synthesis methods are different from the synthesis method of a polyoxyalkylene polymer having a plurality of reactive silicon groups at one terminal of the present invention.

Patent 1801280 JP-A-52-73998 WO2012 / 020560 JP 2005-272733 A JP-A-3-79627

  An object of the present invention is to provide a curable composition having improved curability, restoration rate, weather resistance, and tear strength, and a cured product obtained from the curable composition.

  As a result of intensive studies to solve the above problems, the present inventors have completed the following invention.

  That is, the present invention relates to a reactive silicon group-containing polymer (A) having an average of 1.0 or less reactive silicon groups at one end, and an average of 1.0 to 1.0 reactive silicon groups at one end. The present invention relates to a curable composition containing a reactive silicon group-containing polymer (B) having more than one.

  As far as the present inventors can know, a report example in which a plurality of reactive silicon group-containing polymers at one end and 1.0 or less reactive silicon group-containing polymers at one end are blended in a curable composition. There is no. In the present invention, by adding two types of reactive silicon group-containing polymers having different numbers of reactive silicon groups at the terminal to the curable composition, the curability is improved and the restoration rate of the cured product is increased. , Weather resistance and tear strength can be improved.

The terminal portion of the reactive silicon group-containing polymer (B) is represented by the general formula (1):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, It is a hydrocarbon group which may have an unsubstituted hetero-containing group, each X is independently a hydroxyl group or a hydrolyzable group, a is any one of 1, 2 and 3. It is preferable to have a structure.

The reactive silicon group contained in the reactive silicon group-containing polymer (A) has the general formula (2):
-Si (R ⁶ ) _3-b (X) _b (2)
{In the formula, R ⁶ is the same or different and each is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ') ₃ SiO- ( R 'is a monovalent represents a hydrocarbon group, three R having 1 to 20 carbon atoms' indicates the triorganosiloxy groups may be the same, represented by different may be), R ⁶ is When two or more are present, they may be the same or different. X is each independently a hydroxyl group or a hydrolyzable group. b represents 1, 2 or 3. } It is preferable that it is a reactive silicon group represented by these.

The reactive silicon group contained in the reactive silicon group-containing polymer (A) has the general formula (3):
^{_{-Si (R 7) c (R}} 8) d (X) e (3)
{Wherein c R ^{7 s} each independently have a hydrocarbon group having 1 to 20 carbon atoms as a basic skeleton and at least one hydrogen atom on the 1st to 3rd carbon atoms has an electron withdrawing property. A group substituted by a group. d R ^{8 s} are each independently a hydrocarbon group having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is each independently a hydrocarbon group having 1 to 20 carbon atoms. A triorganosiloxy group represented by: Furthermore, e X's are each independently a hydrolyzable group or a hydroxyl group. c is 1 or 2, d is 0 or 1, and e is 1 or 2, which satisfies c + d + e = 3. } It is preferable that it is a reactive silicon group represented by these.

R ⁷ is preferably an organic group represented by the following general formula (4).
-CR ⁹ _3-f Y _f (4)
{Wherein Y is halogen, —OR ¹⁰ , —NR ¹¹ R ¹² , —N═R ¹³ , —SR ¹⁴ (R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ are each a hydrogen atom or 1 to 20 carbon atoms. Substituted or unsubstituted hydrocarbon group, R ¹³ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, and a cyano group The group to be selected. R ⁹ represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms. f represents 1, 2 or 3. When a plurality of Y and R ⁹ are present, they may be the same or different. }

  It is preferable that General formula (4) is 1 type chosen from a chloromethyl group, a dichloromethyl group, a methoxymethyl group, and an ethoxymethyl group.

  The main chain of the reactive silicon group-containing polymer (A) and / or (B) is preferably a polyoxyalkylene polymer.

  The reactive silicon group-containing polymer (B) preferably has an average of 1.5 or more reactive silicon groups at one terminal.

  An epoxy compound having a carbon-carbon unsaturated bond after the reactive silicon group-containing polymer (B) is reacted with a polymer having a hydroxyl group at the terminal and an alkali metal salt of 0.6 equivalent or more with respect to the hydroxyl group. And then reacting with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond and then introducing a reactive silicon group into the carbon-carbon unsaturated group by a hydrosilylation reaction. Is preferred.

  The reactive silicon group-containing polymer (A) preferably has an average of 1.2 or more reactive silicon groups in one molecule.

  The ratio (A) / (B) of the reactive silicon group-containing polymer (A) to the reactive silicon group-containing polymer (B) is preferably 95/5 to 5/95.

  A cured product can be obtained by curing the curable composition described above.

  According to the present invention, a curable composition having improved curability, restoration rate, weather resistance, and tear strength, and a cured product obtained by curing the curable composition are obtained.

  The present invention provides a reactive silicon group-containing polymer (A) having an average of 1.0 or less reactive silicon groups at one end, and an average of 1.0 reactive silicon groups at one end. The present invention relates to a curable composition containing more reactive silicon group-containing polymer (B), and a cured product obtained from the curable composition.

  In the present invention, the term “end” includes the chain end in the polymer molecular chain and its vicinity. More specifically, it may be defined as a group that substitutes on the number of atoms corresponding to 20%, more preferably 10% from the end of the bonding atoms constituting the polymer molecular chain. In terms of the number of bonded atoms, the terminal site may be defined as the terminal site of 30 atoms, more preferably 20 atoms from the end of the polymer molecular chain.

<< Reactive silicon group-containing polymer (A) >>
The reactive silicon group-containing polymer (A) of the present invention has an average of 1.0 or less reactive silicon groups at one end.

In the present invention, the reactive silicon group contained in the reactive silicon group-containing polymer (A) is represented by the general formula (2):
-Si (R ⁶ ) _3-b (X) _b (2)
{In the formula, R ⁶ is the same or different and each is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ') ₃ SiO- ( R 'is a monovalent represents a hydrocarbon group, three R having 1 to 20 carbon atoms' indicates the triorganosiloxy groups may be the same, represented by different may be), R ⁶ is When two or more are present, they may be the same or different. X is each independently a hydroxyl group or a hydrolyzable group. b represents 1, 2 or 3. } It is preferable that it is a reactive silicon group represented by these.

Furthermore, in this invention, the reactive silicon group which the reactive silicon group containing polymer (A) has is represented by the general formula (3):
^{_{-Si (R 7) c (R}} 8) d (X) e (3)
{Wherein c R ^{7 s} each independently have a hydrocarbon group having 1 to 20 carbon atoms as a basic skeleton and at least one hydrogen atom on the 1st to 3rd carbon atoms has an electron withdrawing property. A group substituted by a group. d R ^{8 s} are each independently a hydrocarbon group having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is each independently a hydrocarbon group having 1 to 20 carbon atoms. A triorganosiloxy group represented by: Furthermore, e X's are each independently a hydrolyzable group or a hydroxyl group. c is 1 or 2, d is 0 or 1, and e is 1 or 2, which satisfies c + d + e = 3. } Is also preferable.

  The average number of reactive silicon groups is 1.0 or less at one end, but it is preferably 0.1 or more and more preferably 0.3 or more at one end. .

  Reactive silicon group-containing polymer (A) The number of reactive silicon groups contained in one molecule is preferably 0.5 or more on average, more preferably 1.0 or more. 1.2 or more, and most preferably 1.5 or more. The upper limit is preferably 4 or less, and more preferably 3 or less.

<Reactive silicon group>
One of the reactive silicon groups of the reactive silicon group-containing polymer (A) suitably used in the present invention is represented by the general formula (2):
-Si (R ⁶ ) _3-b (X) _b (2)
{In the formula, R ⁶ is the same or different and each is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ') ₃ SiO- ( R 'is a monovalent represents a hydrocarbon group, three R having 1 to 20 carbon atoms' indicates the triorganosiloxy groups may be the same, represented by different may be), R ⁶ is When two or more are present, they may be the same or different. X is each independently a hydroxyl group or a hydrolyzable group. b represents 1, 2 or 3. }.

Examples of R ⁶ include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; Preferably, they are a hydrogen atom and a methyl group.

  Examples of X include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group. Of these, alkoxy groups such as a methoxy group and an ethoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable because they are mildly hydrolyzable and easy to handle.

Specific examples of the reactive silicon group (Si (R ⁶ ) _3-b (X) _b ) of the reactive silicon group-containing polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, and tris (2 -Propenyloxy) silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group and the like, but are not limited thereto. Among these, a methyldimethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group are preferable because a cured product having high activity and good mechanical properties can be obtained. From the viewpoint of activity, a trimethoxysilyl group is particularly preferred. From the viewpoint of stability, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are particularly preferred. From the viewpoint of safety during production, methyldiethoxysilyl is preferred. A silyl group and a triethoxysilyl group are particularly preferable, and a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable because of easy production.

The other reactive silicon group of the reactive silicon group-containing polymer (A) preferably used in the present invention is represented by the general formula (3):
^{_{-Si (R 7) c (R}} 8) d (X) e (3)
{Wherein c R ^{7 s} each independently have a hydrocarbon group having 1 to 20 carbon atoms as a basic skeleton and at least one hydrogen atom on the 1st to 3rd carbon atoms has an electron withdrawing property. A group substituted by a group. d R ^{8 s} are each independently a hydrocarbon group having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is each independently a hydrocarbon group having 1 to 20 carbon atoms. A triorganosiloxy group represented by: Furthermore, e X's are each independently a hydrolyzable group or a hydroxyl group. c is 1 or 2, d is 0 or 1, and e is 1 or 2, which satisfies c + d + e = 3. }.

Each R ⁷ is a group in which a hydrocarbon group having 1 to 20 carbon atoms is a basic skeleton and at least one hydrogen atom on the 1st to 3rd carbon atoms is substituted with an electron withdrawing group; However, a substituent represented by the following general formula (4) is preferable because it exhibits higher curability.
-CR ⁹ _3-f Y _f (4)
{Wherein Y is halogen, —OR ¹⁰ , —NR ¹¹ R ¹² , —N═R ¹³ , —SR ¹⁴ (R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ are each a hydrogen atom or 1 to 20 carbon atoms. Substituted or unsubstituted hydrocarbon group, R ¹³ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, and a cyano group The group to be selected. R ⁹ represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms. f represents 1, 2 or 3. When a plurality of Y and R ⁹ are present, they may be the same or different. }

Incidentally, the substituent represented by the general formula (4) is a general formula (3) one R ⁷ in, and a hydrocarbon group having a hetero atom in the 1-position. When two or more R ⁹ are present, the total number of carbon atoms of the two R ⁹ is preferably 0 to 19.

  Y in the general formula (4) is not particularly limited. For example, halogen; oxygen-based substituents such as alkoxy groups and acyloxy groups; nitrogen-based substituents such as amino groups, alkylamino groups, and ureido groups; cyano groups A perfluoroalkyl group and the like.

  More specifically, halogen such as fluorine, chlorine, bromine and iodine; methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-butoxy group, tert-butyloxy group, octoxy group , Alkoxy groups such as lauryloxy group, phenoxy group and benzyloxy group; acyloxy groups such as acetoxy group, propanoyloxy group and benzoyloxy group; amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, Substituted amino groups such as propylamino group, dipropylamino group, diphenylamino group; groups bonded by urethane bond or urea bond such as ureido group, carbamate group; acetyl group, propanoyl group, octanoyl group, laurylyl group, benzoyl group, etc. An acyl group of methoxycarbonyl group, nitro group; cyano group; isocyanato group; sulfonyl group such as methylsulfonyl group and toluenesulfonyl group; trifluoromethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorohexyl group And perfluoroalkyl groups such as perfluorooctyl group; electron-withdrawing aryl groups such as difluorophenyl group and pentafluorophenyl group. Of these, halogens, alkoxy groups, substituted or unsubstituted amino groups, and trifluoromethyl groups are preferred because the resulting polymer exhibits high curability, and halogens, alkoxy groups, substituted or unsubstituted amino groups are preferred. More preferred are halogen and alkoxy groups. In particular, chlorine and methoxy groups are preferable because they exhibit high curability by the curing catalyst for amine compounds. A dialkylamino group is preferred because it exhibits higher curability when a curing catalyst such as carboxylic acids is used.

R ⁷ in the general formula (3) is not particularly limited, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a chloromethyl group, and a dichloromethyl group. 1-chloroethyl group, 2-chloroethyl group, 3-chloropropyl group, 2-chloropropyl group, 1-chloropropyl group, bromomethyl group, iodomethyl group, 3-iodopropyl group, methoxymethyl group, 1-methoxyethyl group , Ethoxymethyl group, phenoxymethyl group, aminomethyl group, N-methylaminomethyl group, N, N-dimethylaminomethyl group, N-ethylaminomethyl group, N, N-diethylaminomethyl group, acetoxymethyl group, methylcarbamate Group, 2-cyanoethyl group and the like.

Examples of R ⁸ include a hydrogen atom; an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; Preferably, they are a hydrogen atom and a methyl group.

  Examples of X include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group. Of these, alkoxy groups such as a methoxy group and an ethoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable because they are mildly hydrolyzable and easy to handle.

As the reactive silicon group (Si (R ⁷ ) _c (R ⁸ ) _d (X) _e ) of the reactive silicon group-containing polymer (A), specifically, (chloromethyl) dimethoxysilyl group, (chloro Methyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group, etc. However, it is not limited to these. Among these, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group show high activity, It is preferable because a cured product having physical properties can be obtained. From the viewpoint of activity, (chloromethyl) dimethoxysilyl group and (methoxymethyl) dimethoxysilyl group are particularly preferred.

<Main chain structure>
The main chain structure of the reactive silicon group-containing polymer (A) may be linear or may have a branched chain.

  The main chain skeleton of the reactive silicon group-containing polymer (A) is not particularly limited, and those having various main chain skeletons can be used. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, Polyoxyalkylene polymers such as polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, isobutylene and isoprene, etc. Copolymer, polychloroprene, polyisoprene, isoprene or a copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or a copolymer of butadiene and acrylonitrile, styrene, and the like. Saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenation of the body; polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones Combined; (meth) acrylic acid ester-based polymer, (meth) acrylic acid-based monomer, vinyl acetate obtained by radical polymerization of (meth) acrylic acid ester-based monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Vinyl polymers such as polymers obtained by radical polymerization of monomers such as acrylonitrile and styrene; graft polymers obtained by polymerizing vinyl monomers in the polymers; polysulfide polymers; ε-caprolactam Polyamide 6 by polycondensation of polyamide 6, hexamethylenediamine and adipic acid by ring-opening polymerization. Of the above polyamides, polyamide 6 · 10 by condensation polymerization of hexaamidediamine and sebacic acid, polyamide 11 by condensation polymerization of ε-aminoundecanoic acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, Polyamide polymers such as copolymer polyamides having two or more components; for example, polycarbonate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride; organic polymers such as diallyl phthalate polymers . Each of the above polymers may be mixed in a block shape, a graft shape or the like. Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers have relatively low glass transition temperatures. The resulting cured product is preferable because it is excellent in cold resistance, and a polyoxyalkylene polymer is more preferable.

  The reactive silicon group-containing polymer (A) may have any one main chain skeleton among the various main chain skeletons described above, and is a mixture of polymers having different main chain skeletons. Also good. Moreover, about a mixture, what manufactured each polymer separately may be mixed, and you may manufacture simultaneously so that it may become arbitrary mixed compositions.

  The number average molecular weight of the reactive silicon group-containing polymer (A) is the number average molecular weight determined by GPC measurement. The molecular weight in terms of polystyrene in GPC is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced is increased, which may be inconvenient in terms of production cost. When the number average molecular weight exceeds 100,000, the viscosity becomes high and the workability is increased. Tend to be inconvenient.

  Regarding the molecular weight of the reactive silicon group-containing polymer (A), the organic polymer precursor before introduction of the reactive silicon group is obtained by measuring the hydroxyl value of JIS K 1557 and the iodine value specified in JIS K 0070. The end group concentration is directly measured by titration analysis based on the principle of the measurement method, and the end group equivalent molecular weight is calculated in consideration of the structure of the organic polymer (degree of branching determined by the polymerization initiator used). You can also The molecular weight of the reactive silicon group-containing polymer (A) in terms of terminal group was determined by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned molecular weight in terms of terminal group. It is also possible to obtain the number average molecular weight obtained by GPC of the group-containing polymer (A) by converting it into a terminal group equivalent molecular weight.

  The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, and further preferably 1.5 or less. Preferably, 1.4 or less is particularly preferable, and 1.2 or less is most preferable. The molecular weight distribution of the reactive silicon group-containing polymer (A) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Synthesis Method of Reactive Silicon Group-Containing Polymer (A)>
Next, a method for synthesizing the reactive silicon group-containing polymer (A) will be described.

(Polyoxyalkylene polymer)
When a polyoxyalkylene polymer is used as the main chain of the reactive silicon group-containing polymer (A), a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is used, and an initiator having a hydroxyl group is used. After obtaining a hydroxyl-terminated polyoxyalkylene polymer by a method of polymerizing an epoxy compound, (i) after converting the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene polymer to a carbon-carbon unsaturated group, silane Reactivity by a method of adding a compound by hydrosilylation reaction, (ii) a method of reacting the obtained hydroxyl-terminated polyoxyalkylene polymer with a compound having both a group that reacts with a hydroxyl group and a reactive silicon group It is preferable to obtain a silicon group-containing polymer (A). Of the above two methods, the method (i) is more preferred because the reaction is simple, the adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable.

  The initiator having a hydroxyl group has at least one hydroxyl group such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, polypropylene monoalkyl ether, etc. Things.

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

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

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

  Examples of the halogenated hydrocarbon compound used in the method (i) include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. It is done.

  When synthesizing the reactive silicon group-containing polymer (A) represented by the general formula (2), examples of the hydrosilane compound used in the method (i) include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, and dichlorophenyl. Halogenated silanes such as silane; alkoxysilanes such as trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane; diacetoxymethylsilane , Acyloxysilanes such as diacetoxyphenylsilane; ketoximate silanes such as bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane, triisopropenyloxy Isopropenyl b silanes such as silane (deacetone type) and the like can be used.

  When the reactive silicon group-containing polymer (A) represented by the general formula (3) is synthesized, examples of the hydrosilane compound used in the method (i) include (chloromethyl) dichlorosilane and (dichloromethyl). ) Halogenated silanes such as dichlorosilane, bis (chloromethyl) chlorosilane, (methoxymethyl) dichlorosilane; (chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, bis (chloro Methyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane , (N, N-diethylaminomethyl Dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [(chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyloxy] dimethyl Alkoxysilanes such as silane, [(diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, [(3,3,3-trifluoropropyl) dimethoxysilyloxy] dimethylsilane; (chloromethyl) diisopropenyloxysilane, (methoxy Isopropenyloxysilanes (deacetone type) such as methyl) diisopropenyloxysilane can be used.

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

  When synthesizing the reactive silicon group-containing polymer (A) represented by the general formula (2), as a compound having both a reactive group and a reactive silicon group that can be used in the method (ii), For example, isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; 3 -Mercaptosilanes such as mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsila And epoxysilanes such as can be used.

  When synthesizing the reactive silicon group-containing polymer (A) represented by the general formula (3), as a compound having both a reactive group and a reactive silicon group that can be used in the method (ii), For example, isocyanate silanes such as 3-isocyanatopropyl (chloromethyl) dimethoxysilane and 3-isocyanatepropyl (methoxymethyl) dimethoxysilane; 3-mercaptopropyl (chloromethyl) dimethoxysilane, 3-mercaptopropyl (methoxymethyl) dimethoxy Mercaptosilanes such as silane; epoxy silanes such as 3-glycidoxypropyl (chloromethyl) dimethoxysilane and 3-glycidoxypropyl (methoxymethyl) dimethoxysilane can be used.

((Meth) acrylic acid ester polymer)
When a (meth) acrylic acid ester polymer is used as the main chain of the reactive silicon group-containing polymer (A), the following methods (i) to (iv) can be used. .
(I) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon group together with a monomer having a (meth) acrylic structure.
(Ii) A method of copolymerizing a monomer having a (meth) acrylic structure in the presence of a compound having a reactive silicon group and a mercapto group as a chain transfer agent.
(Iii) after copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (for example, acrylic acid, 2-hydroxyethyl acrylate) together with a monomer having a (meth) acrylic structure, A method of reacting a compound having a functional group that reacts with a reactive functional group (for example, an isocyanate silane compound).
(Iv) A method in which a monomer having a (meth) acrylic structure is polymerized by a living radical polymerization method such as atom transfer radical polymerization, and then a reactive silicon group is introduced into the molecular chain terminal.

  The method (iv) is preferable because a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained.

<< Reactive silicon group-containing polymer (B) >>
The reactive silicon group-containing polymer (B) of the present invention has an average of more than 1.0 reactive silicon group at one end.

  In the present invention, by adding a reactive silicon group-containing polymer (B) having an average of more than 1.0 reactive silicon group at one terminal, curability, restoration rate, weather resistance, tear strength Will improve. Further, it is predicted that the rise in shear strength and the like will be improved by improving the curability.

  Having an average of more than 1.0 reactive silicon group at one end means that a polymer containing two or more reactive silicon groups is included at one end site. If the average number of reactive silicon groups is more than 1.0 at one terminal, a polymer containing two or more reactive silicon groups at one terminal site and one reaction at one terminal site Both of the polymers containing a functional silicon group may be included. Moreover, the terminal containing two or more reactive silicon groups and the terminal containing one reactive silicon group may be contained in the several terminal of one polymer. Further, a polymer containing two or more reactive silicon groups at one terminal site and a polymer containing a terminal site not having a reactive silicon group may be included.

<Reactive silicon group>
The reactive silicon group-containing polymer (B) may have an average of more than 1.0 reactive silicon groups at one end, but preferably 1.1 or more. More preferably, it is 5 or more, and more preferably 2.0 or more. Further, the upper limit is preferably 5 or less, and more preferably 3 or less.

  Reactive silicon group-containing polymer (B) The terminal structure having two or more reactive silicon groups contained in one molecule is preferably 0.5 or more on average, and 1.0 or more. More preferably, it is 1.1 or more, and most preferably 1.5 or more. The upper limit is preferably 4 or less, and more preferably 3 or less.

  The reactive silicon group-containing polymer (B) may have a reactive silicon group in addition to the terminal site, but a rubber-like cured product having high elongation and having a low elastic modulus only at the terminal site. Since it becomes easy to obtain, it is preferable.

The terminal structure of the reactive silicon group-containing polymer (B) has the general formula (1):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, It is a hydrocarbon group which may have an unsubstituted hetero-containing group, each X is independently a hydroxyl group or a hydrolyzable group, a is any one of 1, 2 and 3. It is preferable that it is a structure.

Examples of R ¹ include CH ₂ OCH ₂ , CH ₂ O, and CH ₂ , and CH ₂ OCH ₂ is preferable.

Examples of R ² and R ⁴ include a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom and a methyl group are preferable.

Examples of R ³ include CH ₂ and CH ₂ CH ₂ , and CH ₂ is preferable.

Examples of R ⁵ include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group, preferably a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group. And more preferably a methyl group or an ethyl group.

Specific examples of the reactive silicon group (SiR ⁵ _3-a Y _a ) of the reactive silicon group-containing polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, and tris (2-propenyloxy) silyl. Group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxy Examples include, but are not limited to, methyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group, and the like. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- A diethylaminomethyl) dimethoxysilyl group is preferred because it exhibits high activity and a cured product having good mechanical properties can be obtained. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl) dimethoxysilyl group, and (methoxymethyl) dimethoxysilyl group are particularly preferable. From the viewpoint of stability, methyldimethoxysilyl group, methyldiethoxysilyl group, triethoxysilyl group Is particularly preferable, and from the viewpoint of safety, a methyldiethoxysilyl group and a triethoxysilyl group are particularly preferable, and a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable because of easy production.

<Main chain structure>
The main chain structure, number average molecular weight, and molecular weight distribution of the reactive silicon group-containing polymer (B) are the same as those of the reactive silicon group-containing polymer (A) described above.

  However, since the synthesis of the reactive silicon group-containing polymer (B) is easy, the main chain is preferably a polyoxyalkylene polymer.

  Further, the reactive silicon group-containing polymer (B) of the present invention is characterized in that the reactive group is localized at the terminal, and therefore the main chain structure is preferably linear.

<Synthesis Method of Reactive Silicon Group-Containing Polymer (B)>
Next, a method for synthesizing the reactive silicon group-containing polymer (B) will be described.

  The reactive silicon group-containing polymer (B) reacts with a carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds at one end of the hydroxyl-terminated polymer obtained by polymerization. It is preferably obtained by reacting a reactive silicon group-containing compound.

  The preferred synthesis method will be described below.

(polymerization)
In the case where a polyoxyalkylene polymer is used as the main chain of the reactive silicon group-containing polymer (B), an initiator having a hydroxyl group using a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex A method of polymerizing an epoxy compound is preferable. The polymerization method of the main chain is preferably the same method as the reactive silicon group-containing polymer (A) described above.

(Introduction of carbon-carbon unsaturated bond)
As a method for introducing two or more carbon-carbon unsaturated bonds at one terminal, an alkali metal salt is allowed to act on a hydroxyl group-containing polymer, and then an epoxy compound having a carbon-carbon unsaturated bond first. It is preferable to use a method in which a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. By using this method, it is possible to efficiently and stably introduce reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain according to the polymerization conditions.

  In the present invention, when an epoxy compound having a carbon-carbon unsaturated bond is reacted with a hydroxyl group-containing polymer, an alkali metal salt is used. By using an alkali metal salt, the terminal sites of all polymers are used. Can be reacted with an epoxy compound having a carbon-carbon unsaturated bond uniformly. When a double metal cyanide complex catalyst is used instead of an alkali metal salt, an epoxy compound having a carbon-carbon unsaturated bond selectively reacts with a polymer having a low molecular weight. This is not preferable because a carbon-carbon unsaturated bond is locally introduced into the terminal portion.

  Examples of the alkali metal salt used in the present invention include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In view of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable. Sodium methoxide is particularly preferred from the standpoint of availability. You may use an alkali metal salt in the state melt | dissolved in the solvent.

  The addition amount of the alkali metal salt used in the present invention is the molar ratio of the polymer to the hydroxyl group, and the lower limit is preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.7 or more and 0.8 or more. preferable. The upper limit is preferably 1.2 or less, and more preferably 1.0 or less. If the addition amount of the alkali metal salt is too small, the reaction does not proceed sufficiently, and if the addition amount is too large, the alkali metal salt remains as an impurity and the side reaction may proceed.

  Alkali metal salts are used to alkoxylate hydroxyl groups in polyoxyalkylene polymers. In order to make this reaction proceed efficiently, water and alcohol other than hydroxyl group-containing polymers are removed from the reaction system. It is preferable to remove. In order to remove, a known method may be used, for example, heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, or the like.

  As temperature at the time of making an alkali metal salt act, 50 to 150 degreeC is preferable and 110 to 140 degreeC is more preferable. As time for making an alkali metal salt act, 10 minutes or more and 5 hours or less are preferable, and 30 minutes or more and 3 hours or less are more preferable.

As an epoxy compound having a carbon-carbon unsaturated bond used in the present invention, in particular, the general formula (5):

A compound represented by the formula (R ¹ and R ² are the same as above) can be preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.

  The addition amount of the epoxy compound having a carbon-carbon unsaturated bond used in the present invention can be any amount in consideration of the introduction amount and reactivity of the carbon-carbon unsaturated bond to the polymer. In particular, the lower limit of the molar ratio with respect to the hydroxyl group contained in the polymer is preferably 0.2 or more, and more preferably 0.5 or more. The upper limit is preferably 5.0 or less, and more preferably 2.0 or less.

  In the present invention, the reaction temperature when the ring-opening addition reaction of the epoxy compound having a carbon-carbon unsaturated bond to the polymer containing a hydroxyl group is preferably 60 ° C. or more and 150 ° C. or less, More preferably, the temperature is 110 ° C. or higher and 140 ° C. or lower. If it is low, the reaction hardly proceeds, and if it is too high, the main chain of the polyoxyalkylene polymer may be decomposed. The reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.

  Examples of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond used in the present invention include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, iodine Methallyl chloride and the like, and it is more preferable to use allyl chloride or methallyl chloride because of easy handling.

  The addition amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the lower limit of the molar ratio to the hydroxyl group contained in the polyoxyalkylene polymer is 0.7 or more. Preferably, 1.0 or more is more preferable. The upper limit is preferably 5.0 or less, and more preferably 2.0 or less.

  As temperature at the time of making the halogenated hydrocarbon compound which has a carbon-carbon unsaturated bond react, 50 to 150 degreeC is preferable and 110 to 140 degreeC is more preferable. The reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.

  The number of hydroxyl groups contained in one molecule of the polymer having a carbon-carbon unsaturated bond obtained after the reaction is preferably 0.3 or less in order to maintain sufficient stability even when stored for a long period of time. 1 or less is more preferable.

(Introduction of reactive silicon groups)
The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(I) A method in which a hydrosilane compound is added to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.
(Ii) a polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of forming a bond by reacting with the carbon-carbon unsaturated bond and a reactive silicon group (also referred to as a silane coupling agent). How to react. Examples of silane coupling agents that react with carbon-carbon unsaturated bonds to form bonds include, but are not limited to, mercapto groups.

  The method (i) is preferable because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the resulting reactive silicon group-containing polymer (B) are stable. The method (ii) has many reaction options, and it is easy and preferable to increase the rate of introduction of reactive silicon groups.

  A part of hydrosilane compound used by the method of (i) is illustrated. Halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, bis (chloromethyl) chlorosilane, (methoxymethyl) dichlorosilane; Silane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) Diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) Ethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane, (N, N-diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [( Chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyloxy] dimethylsilane, [(diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, [(3 , 3,3-trifluoropropyl) dimethoxysilyloxy] dimethylsilane and the like; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; bis (dimethylketoximate) methyl Isopropenyloxysilanes such as lanthanum, ketoxymate silanes such as bis (cyclohexylketoxymate) methylsilane, triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane (Deacetone type).

  The amount of hydrosilane used is preferably from 0.05 to 10 in terms of reactivity in terms of the molar ratio to the unsaturated groups in the polymer that is the precursor (number of moles of hydrosilane / number of moles of unsaturated groups). .3 to 2 are more preferable from the viewpoint of economy.

The hydrosilylation reaction is accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used. For example, platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid; chloroplatinic acid complex composed of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex [eg Pt (CH _{2 = CH 2) 2 (PPh} 3), Pt (CH 2 = CH 2) 2 Cl 2]; platinum - vinylsiloxane complex _{[Pt {(vinyl) Me 2} SiOSiMe 2 (vinyl)}, Pt {Me (vinyl) SiO} ₄ ]; platinum-phosphine complex [Ph (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ]; platinum-phosphite complex [Pt {P (OPh) ₃ } ₄ ] and the like can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex. The temperature conditions for the silylation reaction are not particularly limited, but it is preferable to carry out the reaction under heating conditions for the purpose of lowering the viscosity of the reaction system or improving the reactivity, and the reaction is carried out in the range of 50 ° C to 150 ° C. Is more preferable, and 70 to 120 ° C. is particularly preferable. If the reaction time is longer than necessary, the polymer main chain may deteriorate, and it is preferable to adjust the reaction time together with the temperature. Although the temperature and reaction time are affected by the main chain structure of the polymer to be produced, it is preferably 30 minutes or more and 5 hours or less from the viewpoint of increasing the efficiency of the production process, and more preferably 3 hours or less. preferable.

  Since the reactive silicon group-containing polymer (B) has a high content of reactive silicon groups, the hydrolytic condensation reaction of the reactive silicon groups proceeds at the same time as the hydrosilylation, and the molecular weight is increased. The viscosity may increase during storage for a period of time.

  Therefore, in the production method by hydrosilylation of the reactive silicon group-containing polymer (B), it is possible to improve viscosity and storage stability during silylation by using an orthocarboxylic acid trialkyl ester.

  Specific examples of the orthocarboxylic acid trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate and the like. Trimethyl orthoformate and trimethyl orthoacetate are more preferred.

  The amount of orthocarboxylic acid trialkyl ester used is 0.1 to 10 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the polymer having a carbon-carbon double bond. If the amount used is small, the effect is not sufficiently obtained, and the viscosity of the reactive silicon group-containing polymer (B) may increase. Moreover, when there is too much usage-amount, it is economically disadvantageous, and the work amount of the process of removing orthoester increases.

<Ratio of reactive silicon group-containing polymer (A) and reactive silicon group-containing polymer (B)>
The weight ratio of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B) is not particularly limited, but the reactive silicon group-containing polymer represented by the general formula (2) (A ), (A) / (B) is preferably 95/5 to 5/95, more preferably 85/25 to 55/45. When the weight ratio of the reactive silicon group-containing polymer (B) is less than 5%, it is not preferable because the effect of improving the rapid curing and the restoration rate is difficult to be exhibited, and when it exceeds 95%, the decrease in elongation increases. Therefore, it is not preferable.

  On the other hand, when the reactive silicon group-containing polymer (A) represented by the general formula (3) is used, it is preferable that (A) / (B) is 95/5 to 5/95, More preferably, it is 10-50 / 50, and still more preferably 85 / 15-70 / 30. When the weight ratio of the reactive silicon group-containing polymer (B) is less than 5%, it is not preferable because the effect of improving the rapid curing and the restoration rate is difficult to be exhibited, and when it exceeds 95%, the decrease in elongation increases. Therefore, it is not preferable.

<< Other additives >>
In addition to the reactive silicon group-containing polymers (A) and (B), the composition of the present invention includes, as additives, a silanol condensation catalyst, a filler, an adhesion promoter, a plasticizer, a solvent, a diluent, and a silicate. , Anti-sagging agent, antioxidant, light stabilizer, ultraviolet absorber, physical property modifier, tackifier resin, epoxy group-containing compound, photo-curing material, oxygen-curing material, surface property improving agent, epoxy resin, Other resins, flame retardants and foaming agents may be added. Moreover, you may add various additives to the curable composition of this invention as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, fungicides, and the like. It is done.

<Silanol condensation catalyst>
In the present invention, a silanol condensation catalyst is used for the purpose of accelerating the reaction of hydrolyzing and condensing the reactive silicon groups of the reactive silicon group-containing polymers (A) and (B) and extending or crosslinking the polymer. You may do it.

  As the silanol condensation catalyst, it is already known that many catalysts can be used, and examples thereof include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like.

  Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis ( Ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (Ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), dioctyl tin bis ( Cetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dioctyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate, etc. Can be mentioned. From the recent increase in interest in the environment, it is preferable to use a dioctyltin compound rather than a dibutyltin compound.

  Specific examples of the carboxylate metal salt include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, Examples thereof include manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate. As the carboxylic acid group, the following carboxylic acid and various metals can be combined. As the metal species, divalent tin, bismuth, divalent iron, trivalent iron, zirconium and titanium are preferable because of high activity, and divalent tin is most preferable.

  Specific examples of the amine compound include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, Aliphatic primary amines such as cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine Aliphatic secondary amines such as distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary amines such as amylamine, trihexylamine and trioctylamine; 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), 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] undec-7-ene (OH-DBU), OH -Compounds in which the hydroxyl group of DBU is modified by urethanation, etc., 1,5-diazabicyclo [4,3,0] nonene-5 (DBN), 1,4-diazabicyclo [2,2,2] octane (DABCO), aziridine Nitrogen-containing heterocyclic compounds such as: DBU phenol salt (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), DBU octylate (specifically, trade name: U-CAT SA102) (Product of San Apro)), DBU p-toluenesulfonate (specifically, trade name: U-CAT SA506 (product of San Apro)), DBN octylate (specifically , Trade name: U-CAT 1102 (manufactured by San-Apro)) and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine , Ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) Ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- 1-piperazinyl) ethylamine, xylylenediamine, amines such as 2,4,6-tris (dimethylaminomethyl) phenol; guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide, And biguanides such as 1-phenylbiguanide.

  Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1 Biguanides such as -o-tolyl biguanide and 1-phenyl biguanide are preferable because they exhibit high activity, and aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.

  Further, the amine compound is basic, but an amine compound having a pKa value of the conjugate acid of 11 or more is preferably high in catalytic activity, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are particularly preferable because the pKa value of the conjugate acid is 12 or more and high catalytic activity is exhibited.

  In the present invention, as the amine compound used for the silanol condensation catalyst, an amino group-containing silane coupling agent (sometimes referred to as aminosilane) or a ketimine compound that generates the amine compound by hydrolysis can also be used.

  Specific examples of the carboxylic acid include 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, versatic acid and the like can be mentioned. 2-Ethylhexanoic acid, neodecanoic acid, and versatic acid have high activity and are preferable from the viewpoint of availability. In addition, carboxylic acid derivatives such as carboxylic acid anhydrides, alkyl carboxylates, amides, nitriles, and acyl halides can also be used.

  Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate), Aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), hafnium compounds such as tetrabutoxyhafnium Kind.

Other silanol condensation catalysts include organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride ethylamine complex, etc. Boron trifluoride complex; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane (MEC81 , Commonly known as Ishikawa reagent), potassium hexafluorophosphate, Na ₂ SiF ₆ , K ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ and other fluorine anion-containing compounds.

  A photoacid generator or a photobase generator that generates an acid or a base by light can also be used as a silanol condensation catalyst. Examples of the photoacid generator include triarylsulfonium salts such as p-phenylbenzylmethylsulfonium salt, p-hydroxyphenylbenzylmethylsulfonium salt, triphenylsulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4,4 -Bis [di (β-hydroxyethoxy) phenylsulfonio] phensulfide bishexafluoroantimonate, diphenyliodonium salt, bis (4-tert-butylphenyl) iodonium salt, (4-tert-butoxyphenyl) phenyliodonium salt, Onium salt photoacid generators such as iodonium salts such as (4-methoxyphenyl) phenyliodonium salts, benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthra 2-sulfonate, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, sulfonic acid derivatives such as N- (trifluoromethylsulfonyloxy) naphthylimide, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, Diazomethanes such as methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, carboxylic acid esters, Examples thereof include iron arene complexes.

  The silanol condensation catalyst may be used in combination of two or more different types of catalysts. For example, by using the amine compound and carboxylic acid in combination, an effect of improving the reactivity may be obtained. . The catalytic activity can also be increased by using an acid such as carboxylic acid in combination with a phosphonium salt compound such as tetrabutylphosphonium hydroxide. Moreover, there is a possibility that the reactivity may be improved by using a halogen-substituted aromatic compound such as pentafluorophenol or pentafluorobenzaldehyde and an amine compound in combination.

  The amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). Furthermore, 0.01-15 weight part is more preferable, and 0.01-10 weight part is especially preferable. If the amount of the silanol condensation catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the reaction rate is too fast, and the workable time tends to be deteriorated due to the shortened usable time of the composition, and the storage stability tends to be deteriorated.

  When the reactive silicon group-containing polymer (A) represented by the general formula (3) is used, the amount of the silanol condensation catalyst is reduced or the silanol condensation catalyst having low activity because the activity of the reactive silicon group is high. Can also be used.

<Filler>
Various fillers can be mix | blended with the composition of this invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA powder And fillers such as asbestos, glass fibers and filaments.

  The amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts per 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). Part by weight is preferred.

  An organic balloon or an inorganic balloon may be added to improve the workability (such as sharpness) of the composition. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The balloon is a spherical filler with a hollow inside. The balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. A plurality of types can be mixed, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking.

  Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part of the adhesive containing the thermally expandable fine hollow body, the gas pressure in the shell of the thermally expandable fine hollow body increases and the outer shell material softens, so that the volume expands dramatically. And serves to peel the adhesive interface. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

<Adhesive agent>
An adhesiveness imparting agent can be added to the composition of the present invention.

  As the adhesion-imparting agent, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added.

  Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltris (2-propoxy) silane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropyl. Methyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltriisopropoxysilane, N-β- (β-aminoethyl) aminoethyl-γ-aminopropyltri Methoxysilane, N-6-aminohexyl-γ-aminop Pyrtrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltri Methoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylamino) Amino group-containing silanes such as methyl) trimethoxysilane, bis (3-trimethoxysilylpropyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; γ-isocyanatopropyltrimethoxysilane; Isocyanate group-containing silanes such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane; γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Epoxy group-containing silanes such as β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane, N-β- (carboxy Carboxysilanes such as methyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysila Vinyl type unsaturated group-containing silanes such as γ-chloropropyltrimethoxysilane and other halogen-containing silanes; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; methyl (N-dimethoxymethylsilylmethyl) carbamate , Carbamate silanes such as methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate, etc .; (methoxymethyl) dimethoxymethylsilane, (methoxymethyl) ) Alkoxy group-containing silanes such as trimethoxysilane, (ethoxymethyl) trimethoxysilane, (phenoxymethyl) trimethoxysilane; 3- (trimethoxysilyl) propyl succinic anhydride, 3- (triethoxy Acid anhydride-containing silane such as Lil) propyl succinic anhydride, and the like. In addition, these partial condensates and derivatives thereof, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent.

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

  Moreover, the reaction material of various silane coupling agents can also be used. Reaction products include isocyanate silane and hydroxyl group-containing compound, isocyanate silane and amino group-containing compound; amino silane and acrylic group-containing compound, methacryl group-containing compound (Michael addition reaction product); amino silane and epoxy group Examples include a reaction product with a containing compound, a reaction product with an epoxy silane and a carboxylic acid group-containing compound, and an amino group-containing compound. Reaction products of silane coupling agents such as isocyanate silane and amino silane, amino silane and (meth) acrylic group-containing silane, amino silane and epoxy silane, amino silane and acid anhydride-containing silane can also be used.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

  The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.5-10 weight part is especially preferable.

<Plasticizer>
A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity, slump property of the composition, and mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic carboxylic acid ester compounds such as; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as zil phosphate and tributyl phosphate; Trimellitic ester compounds; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; Process oils; Epoxidized soybean oil, Epoxy benzyl stearate, etc. Epoxy plasticizers, and the like.

  Moreover, a polymeric plasticizer can be used. When a high molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low molecular plasticizer is used. Furthermore, the drying property (paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester 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; number average molecular weight of 500 or more Furthermore, more than 1,000 polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxy group of these polyether polyols Polystyrenes such as polystyrene and polymethyl -α- methyl styrene; group, polyethers such as derivatives obtained by converting the like ether groups polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, polychloroprene, and the like. Various polymers can be provided with physical properties by copolymerizing a reactive group-containing monomer. For example, it is known that the adhesion improvement effect and the elastic recovery rate are improved by using polybutadiene grafted with maleic acid.

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, preferably 10 to 120 parts by weight based on 100 parts by weight of the total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). Part is more preferable, and 20 to 100 parts by weight is particularly preferable. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

<Solvent, Diluent>
A solvent or diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

<Silicate>
Silicates can be added to the composition of the present invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane and alkylalkoxysilane or partial hydrolysis condensates thereof can be used.

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

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  When using a silicate, the amount used is 0.1 to 20 parts by weight, preferably 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B), preferably 0.5 to 10 parts by weight.

<Anti-sagging agent>
An anti-sagging agent may be added to the composition of the present invention as needed to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These anti-sagging agents may be used alone or in combination of two or more.

  The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B).

<Antioxidant>
An antioxidant (antiaging agent) can be used in the composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  The amount of the antioxidant used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight as a total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.2-5 weight part is preferable.

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.

  The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.2-5 weight part is preferable.

  When a photocurable substance is blended in the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144, Tinuvin 770, CHIMASSORB 119FL (all manufactured by BASF); Adekastab LA-57, LA-62, LA-67, LA-63 (all stocks) Examples include light stabilizers such as Sanol LS-770, Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

<Ultraviolet absorber>
An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of UV absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, but benzotriazole is particularly preferable, and commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (above, manufactured by BASF) can be mentioned. 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred. Furthermore, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.

  The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.2-5 weight part is preferable.

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property modifier, For example, alkyl alkoxysilanes, such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Arylalkoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and other alkylisopropenoxysilanes; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

  In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. Further, a derivative of an alkyl alcohol such as hexanol, octanol or decanol which produces a silicon compound which produces a silane monool such as trimethylsilanol by hydrolysis, or trimethylol described in JP-A-11-241029 Mention may be made, for example, of derivatives of polyhydric alcohols having 3 or more hydroxyl groups, such as propane, glycerin, pentaerythritol and sorbitol, which produce silicon compounds that produce silane monools by hydrolysis.

  The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.5-5 weight part is preferable.

<Tackifying resin>
In the present invention, a tackifying resin can be added for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary. The tackifying resin is not particularly limited, and those that are usually used can be used.

  Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols. Resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon) Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  Among these, a terpene-phenol resin is preferable because of high compatibility with the polymer (A) and high adhesion effect. On the other hand, when the color tone is important, a hydrocarbon resin is preferable.

  The amount of the tackifying resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of the total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). More preferably, it is 5-30 parts. When the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and when the amount exceeds 100 parts by weight, the viscosity of the composition may be too high and handling may be difficult.

<Compound containing epoxy group>
In the composition of the present invention, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B).

<Photo-curing substance>
A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like.

  Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, Aronix M-210 of special acrylate (bifunctional), Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, Aronix M-400 (polyfunctional), etc. In addition, a compound containing an average of 3 or more functional groups in one molecule is preferable (all Aronix is a product of Toa Gosei Chemical Co., Ltd.).

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  The photocurable substance is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). It is preferably used in the range of parts by weight, and if it is 0.1 parts by weight or less, there is no effect of improving the weather resistance.

<Oxygen curable substance>
An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.

  The amount of the oxygen curable substance used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). The amount is preferably 0.5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the 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, the oxygen curable substance is preferably used in combination with a photocurable substance.

<Surface property improver>
A surface property improving agent can be added to the composition of the present invention. Examples of surface property improvers include long-chain alkylamines such as laurylamine, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, tris (2,4-di-t-butylphenyl). ) Phosphorus compounds such as phosphites, oxazolidine compounds and the like.

  The amount of the surface property improving agent used is in the range of 0.3 to 10 parts by weight with respect to 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). It is preferable to do this.

<Epoxy resin>
An epoxy resin can be used in combination with the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies 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.

  The total use ratio of these epoxy resins, the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B) is (A) + (B) / epoxy resin = 100 in weight ratio. / 1 to 1/100. When the ratio of (A) + (B) / epoxy resin is less than 1/100, it is difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and (A) + (B) / epoxy resin. If the ratio exceeds 100/1, the strength of the polymer cured product becomes insufficient. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The total of the reactive silicon group-containing (A) and the reactive silicon group-containing polymer (B) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. Good. On the other hand, in the case of improving the strength of the cured product, 1 to 200 parts by weight of the epoxy resin with respect to a total of 100 parts by weight of the reactive silicon group-containing (A) and the reactive silicon group-containing polymer (B), More preferably, 5 to 100 parts by weight are used.

  When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

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

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

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and it may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.

  These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

<Flame Retardant>
A flame retardant such as a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added to the composition of the present invention. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). used.

<Foaming agent>
The composition of the present invention can be used as a foam material using a foaming agent. For example, a liquefied gas such as butane, propane, ethane, methane or dimethyl ether can be used as an aerosol propellant. Moreover, you may use compressed gas, such as air, oxygen, nitrogen, and a carbon dioxide. A propellant containing pentane, hexane, or heptane can be used as a hydrocarbon solvent having a boiling range of 10 to 100 ° C. Moreover, a siloxane oxyalkylene copolymer can be used as a foam stabilizer. The amount of the foaming agent used is 5 to 100 ml, preferably 5 to 50 ml, more preferably 5 to 100 g in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). Can be used in the range of ~ 20 ml.

<< Preparation of curable composition >>
The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the organic polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to add a silanol condensation catalyst to the main agent containing an organic polymer having a reactive silicon group, so even if some moisture is contained in the compounding agent. Although there is little concern about the viscosity increase or gelation of the blend, it is preferable to perform dehydration drying when long-term storage stability is required. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of the silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 100 parts by weight in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). In the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

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

  The curable composition of the present invention is a moisture-reactive composition in which the reaction proceeds by moisture, but is a so-called dual curable composition used in combination with a thermosetting resin, a photocurable resin, or a radiation curable resin. It can also be used as Specifically, it is possible to use a curable resin utilizing an ene-thiol addition reaction, a radical polymerization reaction of a (meth) acryl group, a ring-opening polymerization reaction of an epoxy group, an addition reaction by hydrosilylation, a urethanization reaction, or the like. it can.

<< Usage >>
The composition of the present invention is suitable for use as a curable composition or a pressure-sensitive adhesive composition, and is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, and a waterproof coating material. It can be used for mold preparations, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spray materials, etc. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.

  Also, electrical / electronic component materials such as solar cell backside sealing materials, electrical / electronic components such as insulation coating materials for electric wires and cables, electrical insulation materials for devices, acoustic insulation materials, elastic adhesives, binders, contact type Adhesives, spray-type sealing materials, crack repair materials, tile adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical equipment Sealing materials, dental impression materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials , Potting agents for electrical and electronic use, films, gaskets, concrete reinforcements, adhesives for temporary fixing, various molding materials, and meshed glass and laminated glass end faces Liquid sealant used in sealing parts for rust prevention and waterproofing of cutting parts, large vehicle parts such as automobile parts, trucks, buses, train car parts, aircraft parts, marine parts, electrical parts, various machine parts, etc. It can be used for various purposes. Taking automobiles as an example, it can be used in a wide variety of applications such as plastic covers, trims, flanges, bumpers, window attachments, interior attachments, and exterior attachments. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, leather, textile products, adhesives for bonding fabrics, paper, board and rubber, reactive post-crosslinking pressure sensitive adhesives, direct It can also be used as a sealing material for glazing, a sealing material for double-glazed glass, a sealing material for SSG method, a sealing material for building working joints, a civil engineering material, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape or an adhesive sheet.

  Examples of the method of the present invention will be specifically described below, but the present invention is not limited to these examples.

  The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.

Liquid feeding system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C
The molecular weight in terms of end groups in the examples is determined by measuring the hydroxyl value by the measuring method of JIS K 1557 and the iodine value by the measuring method of JIS K 0070, and calculating the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). This is the molecular weight determined in consideration.

The average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer (Q) shown in the examples was calculated by the following formula.
(Average number of introductions) = [Unsaturated group concentration of polymer (Q) determined from iodine value (mol / g) −Unsaturated group concentration of precursor polymer (P) determined from iodine value (mol / g)] / [Hydroxyl concentration of precursor polymer (P) determined from hydroxyl value (mol / g)].

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

(Synthesis Example 1)
Polyoxypropylene glycol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight having a hydroxyl group at both ends is 27,900 (in terms of end group) Polyoxypropylene (P-1) having a molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21 was obtained. 1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene (P-1). After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was further added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, a polyoxypropylene polymer (Q-1) having an allyl group at the terminal site was obtained. To 500 g of this polymer (Q-1), 150 μl of platinum divinyldisiloxane complex solution was added, and 4.8 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure, whereby a poly (polysiloxane having a number average molecular weight of 28,500 having an average of 1.0 or less dimethoxymethylsilyl group at the terminal is obtained. Oxypropylene (A-1) was obtained. The polymer (A-1) was found to have an average of 0.8 dimethoxymethylsilyl groups at one end and an average of 1.6 per molecule.

(Synthesis Example 2)
Polyoxypropylene glycol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight having hydroxyl groups at both ends is 14,300 (in terms of end groups) Polyoxypropylene (P-2) having a molecular weight of 9,100) and a molecular weight distribution of Mw / Mn = 1.21 was obtained. 1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene (P-2). After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was added to the hydroxyl group of the polymer (P-2) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, a polyoxypropylene polymer (Q-2) having an allyl group at the terminal site was obtained. To 500 g of this polymer (Q-2), 150 μl of platinum divinyldisiloxane complex solution was added, and 8.4 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain a polysiloxane having a number average molecular weight of 14,600 having an average of 1.0 or less dimethoxymethylsilyl group at the terminal. Oxypropylene (A-2) was obtained. The polymer (A-2) was found to have an average of 0.8 dimethoxymethylsilyl groups at one end and an average of 1.6 per molecule.

(Synthesis Example 3)
A polyoxypropylene triol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 24,600 having a hydroxyl group at the terminal (terminal group equivalent molecular weight) 17, 400), and polyoxypropylene (P-3) having a molecular weight distribution Mw / Mn = 1.31 was obtained. 1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene (P-3). After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was added to the hydroxyl group of the polymer (P-3) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, a polyoxypropylene polymer (Q-3) having an allyl group at the terminal site was obtained. To 500 g of this polymer (Q-3), 150 μl of platinum divinyldisiloxane complex solution was added, and 6.4 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure, whereby a poly (polystyrene) having a number average molecular weight of 26,200 having an average of 1.0 or less dimethoxymethylsilyl group at the terminal is obtained. Oxypropylene (A-3) was obtained. The polymer (A-3) was found to have an average of 0.7 dimethoxymethylsilyl groups at one end and an average of 2.2 per molecule.

(Synthesis Example 4)
1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis Example 1. After distilling off methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. As described above, polyoxypropylene (Q-4) having a terminal structure having an average of more than 1.0 carbon-carbon unsaturated bonds at one terminal was obtained. The polymer (Q-4) was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

  50 μl of platinum divinyldisiloxane complex solution is added to 500 g of polyoxypropylene (Q-4) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, and dimethoxymethylsilane 9. 6 g was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average having more than 1.0 dimethoxymethylsilyl groups on one end on average. Polyoxypropylene (B-1) having a molecular weight of about 28,500 was obtained. The polymer (B-1) was found to have an average of 1.7 dimethoxymethylsilyl groups at one end and an average of 3.4 per molecule.

(Synthesis Example 5)
1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-2) obtained in Synthesis Example 2. After distilling off methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 1.0 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. As described above, polyoxypropylene (Q-5) having an average of more than 1.0 carbon-carbon unsaturated bond at one end was obtained. The polymer (Q-5) was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

  50 μl of platinum divinyldisiloxane complex solution is added to 500 g of polyoxypropylene (Q-5) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site thus obtained, and dimethoxymethylsilane 18. 2 g was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average having more than 1.0 dimethoxymethylsilyl groups on one end on average. Polyoxypropylene (B-2) having a molecular weight of 15,300 was obtained. The polymer (B-2) was found to have an average of 1.6 dimethoxymethylsilyl groups at one end and an average of 3.2 per molecule.

(Synthesis Example 6)
1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-3) obtained in Synthesis Example 3. After distilling off methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-3) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. As described above, polyoxypropylene (Q-6) having an average of more than 1.0 carbon-carbon unsaturated bonds at one terminal was obtained. The polymer (Q-6) was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

  50 μl of platinum divinyldisiloxane complex solution is added to 500 g of polyoxypropylene (Q-6) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, and dimethoxymethylsilane 12. 6 g was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average having more than 1.0 dimethoxymethylsilyl groups on one end on average. Polyoxypropylene (B-3) having a molecular weight of 27,500 was obtained. The polymer (B-3) was found to have an average of 1.6 dimethoxymethylsilyl groups at one end and an average of 4.8 per molecule.

(Examples 1-4, Comparative Examples 1-3)
For a total of 100 parts by weight of the polymers (A) and (B) listed in Table 1, 55 parts by weight of DIDP (manufactured by Kyowa Hakko Kogyo Co., Ltd .: diisodecyl phthalate), Shiraka Hana CCR (manufactured by Shiroishi Calcium Co., Ltd.) 120 parts by weight of precipitated calcium carbonate), 20 parts by weight of Taipei R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide), 2 parts by weight of Disparon 6500 (manufactured by Enomoto Chemical Co., Ltd .: fatty acid amide wax), TINUVIN 327 (manufactured by BASF: 2) -(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole) 1 part by weight, Sanol LS770 (manufactured by Ciba Specialty Chemicals: bis (2,2,6,6-tetramethyl-4) -Piperidyl) sebacate) 1 part by weight was mixed and dispersed uniformly using three rolls. Then, 2 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (manufactured by Momentive: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane), U-220H ( 1 part by weight of Nitto Kasei Co., Ltd. product: dibutyltin bisacetylacetonate) was added and mixed thoroughly with a spatula, and then uniformly mixed and defoamed using a rotating and rotating mixer.

(Skinning time)
The obtained composition was filled into a mold having a thickness of about 5 mm using a spatula, the time when the surface was flattened was set as the curing start time, the surface was touched with the spatula, and the evaluation composition adhered to the spatula. Curing time was measured with the time when it disappeared as the skinning time. The results are shown in Table 1.

(Hardened physical properties)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a No. 3 dumbbell mold and subjected to a tensile strength test at 23 ° C. and 50% RH to measure the modulus at 100% elongation, the strength at break, and the elongation. The measurement was performed using a Shimadzu autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in Table 1.

(Restoration rate)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product is punched out into a No. 3 dumbbell shape, marked lines at intervals of 20 mm are drawn on the constricted portion of the dumbbell-shaped cured product, and fixed in an extended state so that the distance between the marked lines becomes 40 mm. For 24 hours. After fixing, the restoration rate after 1 hour, 1 day, and 1 week was measured. The restoration rate was calculated by the following formula. The results are shown in Table 1.

    Restoration rate (%) = (40-distance between marked lines (mm)) / 20.

(Weather resistance test)
A sheet-like cured product having a thickness of about 3 mm was produced in the same manner as the restoration rate measurement. Then, this sheet | seat was installed in the sunshine carbon arc lamp type | mold accelerated weathering tester (Suga Test Instruments Co., Ltd. make, model number S80) which is an accelerated weathering tester. A weather resistance test was conducted under the conditions of a black panel temperature of 63 ° C., a temperature of 50 ° C., and a spraying time of 18 minutes for 120 minutes, and the surface state of the sheet for 600 hours and 1000 hours is defined by the ISO standard. ) And the numerical value (S value) were utilized, the product value of Q value and S value was used as a scale representing the degree of surface deterioration, and the QS value was set to quantitatively represent the cracked state. The results are shown in Table 1. The QS value is represented by A for 0, B for greater than 0 and 10 or less for B, C for greater than 15 and less than 15 and D for greater than 15 and 20 or less.

  In Examples 1 and 2 in which B-1 as the polymer (B) was added to A-1 as the polymer (A), the curing rate was higher than that in Comparative Example 1 in which only A-1 was used as the polymer. (Skinning time), restoration rate of cured product, and weather resistance test results are good. Similarly, in Examples 3 and 4, the curing speed, the restoration rate of the cured product, and the weather resistance test results are better than those in Comparative Examples 2 and 3.

(Examples 5 and 6, Comparative Example 4)
90 parts by weight of DIDP (manufactured by Kyowa Hakko Kogyo Co., Ltd .: diisodecyl phthalate) and Neolite SP (manufactured by Takehara Chemical Industry Co., Ltd.) with respect to 100 parts by weight of the polymers (A) and (B) listed in Table 2 : Precipitated calcium carbonate) 160 parts by weight, Whiten SB (manufactured by Shiraishi Kogyo Co., Ltd .: heavy calcium carbonate) 54 parts by weight, Taipei R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide), 20 parts by weight 2 parts by weight of Chemical Co., Ltd .: fatty acid amide wax), 1 part by weight of Tinuvin 326 (manufactured by BASF: 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol) , 1 part by weight of Sanol LS770 (Ciba Specialty Chemicals: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate) was mixed. It was uniformly dispersed using a 3-roll. Thereafter, 3 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (manufactured by Momentive: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane), U-220H ( 2 parts by weight of Nitto Kasei Co., Ltd .: dibutyltin bisacetylacetonate) was added and mixed thoroughly with a spatula, and then uniformly mixed and defoamed using a rotating and rotating mixer.

(Tear test)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a tear test dumbbell type (JIS A type), and a tear test was performed at 23 ° C. and 50% RH. The measurement was performed using a Shimadzu autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in Table 2.

  In Examples 5 and 6 in which B-1 as the polymer (B) was added to A-1 as the polymer (A), the tear strength was higher than that in Comparative Example 4 in which only A-1 was used as the polymer. Has improved.

(Synthesis Example 7)
To 500 g of the polyoxypropylene polymer (Q-1) having an allyl group obtained in Synthesis Example 1, 150 μl of a platinum divinyldisiloxane complex solution is added and stirred while (methoxymethyl) dimethoxysilane (( _{CH 3 OCH 2) (CH 3} O) 2 SiH) was slowly added dropwise 6.5 g. After reacting at 90 ° C. for 2 hours, unreacted (methoxymethyl) dimethoxysilane is distilled off under reduced pressure to have an average of 1.0 or less (methoxymethyl) dimethoxysilyl group at one end. Polyoxypropylene (A-4) having a number average molecular weight of about 28,200 was obtained. The polymer (A-4) was found to have an average of 0.8 (methoxymethyl) dimethoxysilyl groups at one end and an average of 1.6 per molecule.

(Synthesis Example 8)
To 500 g of polyoxypropylene (Q-4) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site obtained in Synthesis Example 4, 50 μl of platinum divinyldisiloxane complex solution is added and stirred while stirring. 10.5 g of methoxysilane was slowly added dropwise. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain a number having an average of more than 1.0 trimethoxysilyl groups at one end. Polyoxypropylene (B-4) having an average molecular weight of about 28,500 was obtained. The polymer (B-4) was found to have an average of 1.7 trimethoxysilyl groups at one end and an average of 3.4 per molecule.

(Synthesis Example 9)
50 μl of a platinum divinyldisiloxane complex solution is added to 500 g of polyoxypropylene (Q-4) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site obtained in Synthesis Example 4 while stirring ( 11.7 g of (methoxymethyl) dimethoxysilane was slowly added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted (methoxymethyl) dimethoxysilane was distilled off under reduced pressure, whereby an average of more than 1.0 (methoxymethyl) per one end was obtained. Polyoxypropylene (B-5) having a dimethoxysilyl group and a number average molecular weight of about 28,400 was obtained. The polymer (B-5) was found to have an average of 1.7 (methoxymethyl) dimethoxysilyl groups at one end and an average of 3.4 per molecule.

(Examples 7 and 8, Comparative Example 5)
For a total of 100 parts by weight of the polymers (A) and (B) listed in Table 3, 55 parts by weight of DIDP (manufactured by Kyowa Hakko Kogyo Co., Ltd .: diisodecyl phthalate), Shiraka Hana CCR (manufactured by Shiraishi Calcium Co., Ltd.): 120 parts by weight of precipitated calcium carbonate), 20 parts by weight of Taipei R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide), 2 parts by weight of Disparon 6500 (manufactured by Enomoto Chemical Co., Ltd .: fatty acid amide wax), TINUVIN 327 (manufactured by BASF: 2) -(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole) 1 part by weight, Sanol LS770 (manufactured by Ciba Specialty Chemicals: bis (2,2,6,6-tetramethyl-4) -Piperidyl) sebacate) 1 part by weight was mixed and dispersed uniformly using three rolls. Thereafter, 2 parts by weight of A-171 (Mentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (Mentive: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane), 1-phenylguanidine After adding 0.55 part by weight of 45% Nn-butylbenzenesulfonamide solution (Nippon Carbide Co., Ltd .: PhG / BBSA) and mixing well with a spatula, it was mixed and defoamed uniformly using a rotating and rotating mixer. .

(Skinning time)
The obtained composition was filled into a mold having a thickness of about 5 mm using a spatula, the time when the surface was flattened was set as the curing start time, the surface was touched with the spatula, and the evaluation composition adhered to the spatula. Curing time was measured with the time when it disappeared as the skinning time. The results are shown in Table 3.

(Restoration rate)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product is punched out into a No. 3 dumbbell shape, marked lines at intervals of 20 mm are drawn on the constricted portion of the dumbbell-shaped cured product, and fixed in an extended state so that the distance between the marked lines becomes 40 mm. For 24 hours. After fixing, the restoration rate after 1 hour, 1 day, and 1 week was measured. The restoration rate was calculated by the following formula. The results are shown in Table 3.

    Restoration rate (%) = (40-distance between marked lines (mm)) / 20.

(Weather resistance test)
A sheet-like cured product having a thickness of about 3 mm was produced in the same manner as the restoration rate measurement. Then, this sheet | seat was installed in the sunshine carbon arc lamp type | mold accelerated weathering tester (Suga Test Instruments Co., Ltd. make, model number S80) which is an accelerated weathering tester. A weather resistance test was conducted under the conditions of a black panel temperature of 63 ° C., a temperature of 50 ° C. and a spraying time of 120 minutes for 120 minutes, and the surface state of the sheet for 600 hours and 1000 hours was defined by the ISO standard. ) And the numerical value (S value) were utilized, the product value of Q value and S value was used as a scale representing the degree of surface deterioration, and the QS value was set to quantitatively represent the cracked state. The results are shown in Table 3. The QS value is represented by A for 0, B for greater than 0 and 10 or less for B, C for greater than 15 and less than 15 and D for greater than 15 and 20 or less.

Examples 7 and 8 in which B-4 and B-5 as polymers (B) were added to A-4 as a polymer (A) were compared with Comparative Example 5 using only A-4 as a polymer. The curing rate (skinning time), the restoration rate of the cured product, and the weather resistance test results are good.

Claims (7)

Reactive silicon group-containing polymer (A) having an average of 1.0 or less reactive silicon groups at one end composed of 30 atoms from the end of the polymer molecular chain , and the end of the polymer molecular chain Containing a reactive silicon group-containing polymer (B) having an average of more than 1.0 reactive silicon groups at one end composed of 30 to 30 atoms ,
The main chain of the reactive silicon group-containing polymers (A) and (B) is a polyoxyalkylene polymer,
The reactive silicon group-containing polymer (B) has the general formula (1) as a terminal site:

(In the formula, R ¹ is each independently a divalent linking group having 1 to 6 carbon atoms, R ³ is CH ₂ , and the atoms bonded to adjacent carbon atoms are carbon, oxygen, or nitrogen, respectively. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is each independently 1 carbon atom number. To a hydrocarbon group which may have a substituted or unsubstituted hetero-containing group of 20 to 20. X is independently a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3. .) Having a structure represented by
The reactive silicon group-containing polymer (A) has the general formula (2):
-Si (R ⁶ ) _3-b (X) _b (2)
{In the formula, R ⁶ is the same or different and each is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ') ₃ SiO- ( R 'is a monovalent represents a hydrocarbon group, three R having 1 to 20 carbon atoms' indicates the triorganosiloxy groups may be the same, represented by different may be), R ⁶ is When two or more are present, they may be the same or different. X is each independently a hydroxyl group or a hydrolyzable group. b represents 1, 2 or 3. } Or a reactive silicon group represented by the general formula (3):
_{^{-Si (R 7) c (R}} 8) d (X) e (3)
{Wherein c R ^{7 s} each independently have a hydrocarbon group having 1 to 20 carbon atoms as a basic skeleton and at least one hydrogen atom on the 1st to 3rd carbon atoms has an electron withdrawing property. A group substituted by a group. d R ^{8 s} are each independently a hydrocarbon group having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is each independently a hydrocarbon group having 1 to 20 carbon atoms. A triorganosiloxy group represented by: Furthermore, e X's are each independently a hydrolyzable group or a hydroxyl group. c is 1 or 2, d is 0 or 1, and e is 1 or 2, which satisfies c + d + e = 3. } The curable composition characterized by having a reactive silicon group represented by these . The curable composition according to claim 1 , wherein R ⁷ is an organic group represented by the following general formula (4).
-CR ⁹ _3-f Y _f (4)
{Wherein Y is halogen, —OR ¹⁰ , —NR ¹¹ R ¹² , —N═R ¹³ , —SR ¹⁴ (R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ are each a hydrogen atom or 1 to 20 carbon atoms. Substituted or unsubstituted hydrocarbon group, R ¹³ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, and a cyano group The group to be selected. R ⁹ represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms. f represents 1, 2 or 3. When a plurality of Y and R ⁹ are present, they may be the same or different. } The curable composition according to claim 2 , wherein the general formula (4) is one selected from a chloromethyl group, a dichloromethyl group, a methoxymethyl group, and an ethoxymethyl group. The curable composition according to any one of claims 1 to 3 , wherein the reactive silicon group-containing polymer (B) has an average of 1.5 or more reactive silicon groups at one terminal. The curable composition according to any one of claims 1 to 4 , wherein the reactive silicon group-containing polymer (A) has an average of 1.2 or more reactive silicon groups in one molecule. The ratio of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B) (A) / ( B) is any one of claim 1 to 5, which is a 95 / 5-5 / 95 The curable composition according to 1. Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-6 .