WO2015080067A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2015080067A1
WO2015080067A1 PCT/JP2014/081000 JP2014081000W WO2015080067A1 WO 2015080067 A1 WO2015080067 A1 WO 2015080067A1 JP 2014081000 W JP2014081000 W JP 2014081000W WO 2015080067 A1 WO2015080067 A1 WO 2015080067A1
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group
reactive silicon
containing polymer
polymer
carbon
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PCT/JP2014/081000
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English (en)
Japanese (ja)
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達郎 春増
秀治 城野
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株式会社カネカ
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Priority to JP2015550915A priority Critical patent/JP6096320B2/ja
Publication of WO2015080067A1 publication Critical patent/WO2015080067A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • 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).
  • the main chain skeleton has various polymers such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester copolymer.
  • 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 using an alkali catalyst such as KOH polymerization 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.
  • a reactive silicon group-containing polyoxyalkylene polymer can be obtained (Patent Document 2).
  • Patent Document 3 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.
  • Patent Documents 4 and 5 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.
  • 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.
  • 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.
  • 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) ⁇
  • R 6 s are the same or different and each represents 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— (wherein R 'is a monovalent represents a hydrocarbon group, three R of 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 carbon number 1 to 20 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 general formula (4) is preferably one kind selected 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 end.
  • 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.
  • 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.
  • the term “end” includes the chain end in the polymer molecular chain and the vicinity thereof. 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.
  • 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.
  • 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) ⁇
  • R 6 s are the same or different and each represents 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 of 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 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) ⁇
  • 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.
  • 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.
  • R 6 s are the same or different and each represents 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 of 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. ⁇ .
  • R 6 examples 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.
  • 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.
  • the reactive silicon group (Si (R 6 ) 3-b (X) b ) of the reactive silicon group-containing polymer (A) include trimethoxysilyl group, triethoxysilyl group, tris (2 -Propenyloxy) silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group and the like, but are not limited thereto.
  • 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.
  • a trimethoxysilyl group is particularly preferred.
  • a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are particularly preferred.
  • 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) ⁇
  • 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.
  • 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;
  • a substituent represented by the following general formula (4) is preferable because it exhibits higher curability.
  • 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 carbon number 1 to 20 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.
  • 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.
  • 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.
  • 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.
  • halogen such as fluorine, chlorine, bromine and iodine
  • Alkoxy groups such as lauryloxy group, phenoxy group and benzyloxy group
  • acyloxy groups such as acetoxy group, propanoyloxy group and benzoyloxy group
  • An acyl group a methoxycarbonyl group alkoxycarbonyl group such as tert-butyloxycarbonyl 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.
  • 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.
  • 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.
  • R 8 examples 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.
  • 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.
  • 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.
  • chloromethyl dimethoxysilyl group specifically, (chloromethyl) dimethoxysilyl group, (chloro Methyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, etc.
  • (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group showed high activity and good mechanical properties. 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.
  • 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.
  • polyoxyethylene, polyoxypropylene, polyoxybutylene, Polyoxyalkylene polymers such as polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, isobutylene and isoprene, etc.
  • Copolymers polychloroprene, polyisoprene, isoprene or copolymers of butadiene with acrylonitrile and / or styrene, polybutadiene, isoprene or copolymers of butadiene with acrylonitrile and styrene, and the polyolefins thereof Saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenation of the polymers; 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 ethyl (meth) acrylate, butyl (meth) acrylate and other (meth) acrylic acid ester monomers Vinyl polymers such as polymers obtained by radical polymerization of monomers such as acrylonitrile and
  • Each of the above polymers may be mixed in a block shape, a graft shape or the like.
  • 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 obtained by GPC measurement is used for the number average molecular weight of the reactive silicon group-containing polymer (A).
  • 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.
  • 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.
  • the number average molecular weight exceeds 100,000, the viscosity becomes high and the workability is increased. Tend to be inconvenient.
  • 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).
  • 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.
  • 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.
  • a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is used, and an initiator having a hydroxyl group is used.
  • a hydroxyl group-terminated polyoxyalkylene polymer After obtaining a hydroxyl group-terminated polyoxyalkylene polymer by a method of polymerizing an epoxy compound, (i) after converting the hydroxyl group of the obtained hydroxyl group-terminated polyoxyalkylene polymer to a carbon-carbon unsaturated group, 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.
  • the epoxy compound examples 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.
  • 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.
  • halogenated hydrocarbon compound used in the method (i) examples include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. It is done.
  • 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, and triisopropenylo Isopropenyl b silanes such as Shishiran (deacetone type) and the like can be used.
  • alkoxysilanes such as trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dime
  • 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) ) Dime
  • the hydrosilylation reaction used in the method (i) is accelerated by various catalysts.
  • the hydrosilylation catalyst known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used.
  • 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 - 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
  • isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; 3 -Mercaptosilanes such as mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane And epoxy silanes such as emission can be used.
  • isocyanate silanes such as 3-isocyanatopropyl (chloromethyl) dimethoxysilane, 3-isocyanatopropyl (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.
  • 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.
  • 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.
  • 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.
  • R 1 examples include CH 2 OCH 2 , CH 2 O, and CH 2 , and CH 2 OCH 2 is preferable.
  • R 2 and R 4 examples include a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom and a methyl group are preferable.
  • R 3 examples include CH 2 and CH 2 CH 2 , and CH 2 is preferable.
  • R 5 examples include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group, and a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group are preferable. And more preferably a methyl group or an ethyl group.
  • reactive silicon group (SiR 5 3-a Y a ) of the reactive silicon group-containing polymer (B) include trimethoxysilyl group, triethoxysilyl group, and tris (2-propenyloxy) silyl.
  • 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.
  • trimethoxysilyl group, (chloromethyl) dimethoxysilyl group, and (methoxymethyl) dimethoxysilyl group are particularly preferable.
  • 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.
  • the main chain is preferably a polyoxyalkylene polymer.
  • the reactive silicon group-containing polymer (B) of the present invention is characterized in that a reactive group is localized at the terminal, the main chain structure is preferably linear.
  • the reactive silicon group-containing polymer (B) reacts with a carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds into one terminal of the hydroxyl-terminated polymer obtained by polymerization. It is preferably obtained by reacting a reactive silicon group-containing compound.
  • 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.
  • an alkali metal salt is used when a hydroxyl-terminated polymer is reacted with an epoxy compound having a carbon-carbon unsaturated bond.
  • an alkali metal salt By using an alkali metal salt, the terminal sites of all polymers are used. An epoxy compound having a carbon-carbon unsaturated bond can be reacted uniformly.
  • 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.
  • alkali metal salt used in the present invention examples include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
  • 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
  • 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.
  • water and alcohol other than hydroxyl group-containing polymers are removed from the reaction system. It is preferable to remove.
  • a known method may be used, for example, heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, or the like.
  • the temperature at which the alkali metal salt is allowed to act is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 140 ° C. or lower.
  • 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.
  • a compound represented by the formula (R 1 and R 2 are the same as above) can be preferably used.
  • 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.
  • 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.
  • 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 higher and 150 ° C. or lower. 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.
  • halogenated hydrocarbon compound having a carbon-carbon unsaturated bond examples 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 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.
  • the temperature at which the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 140 ° C. or lower.
  • 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.
  • 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.
  • 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.
  • 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)
  • 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.
  • known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used.
  • 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 - 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
  • a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.
  • the temperature conditions for the silylation reaction are not particularly limited, but the reaction is preferably carried out under heating conditions for the purpose of reducing 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.
  • the reactive silicon group-containing polymer (B) 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.
  • orthocarboxylic acid trialkyl ester can improve the thickening and storage stability during silylation.
  • orthocarboxylic acid trialkyl ester examples 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.
  • 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.
  • 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.
  • (A) / (B) is preferably 95/5 to 5/95, It is more preferably 10 to 50/50, and still more preferably 85/15 to 70/30.
  • 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.
  • 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.
  • a silanol condensation catalyst for example, 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.
  • examples of such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors
  • 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.
  • 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.
  • organic tin compound examples 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, dibuty
  • carboxylate metal salt examples 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.
  • carboxylic acid group the following carboxylic acid and various metals can be combined.
  • 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.
  • amine compound examples 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
  • 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.
  • aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness.
  • aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.
  • the amine compound is basic, but an amine compound in which the pKa value of the conjugate acid is 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.
  • 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.
  • carboxylic acid examples 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, Examples include 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.
  • 2-Ethylhexanoic acid, neodecanoic acid, and versatic acid have high activity and are preferable from the viewpoint of availability.
  • carboxylic acid derivatives such as carboxylic acid anhydrides, alkyl carboxylates, amides, nitriles, and acyl halides can also be used.
  • 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 tetrabutoxyhafniumkind.
  • titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylace
  • 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.
  • MEC81 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane
  • a photoacid generator or photobase generator that generates an acid or a base by light can also be used as a silanol condensation catalyst.
  • 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 ( ⁇ -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) pheny
  • the silanol condensation catalyst may be used in combination of two or more different types of catalysts.
  • 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.
  • 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 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly 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.
  • 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.
  • 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.
  • 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
  • the use amount of the filler is preferably 1 to 300 parts by weight, particularly 10 to 200 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 by weight is preferred.
  • Organic balloons and inorganic balloons may be added to improve the workability of the composition (such as sharpness). These fillers can be surface-treated, and may be used alone or in combination of two or more.
  • the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, it is preferably 5 to 300 ⁇ m.
  • the balloon is a spherical filler with a hollow interior.
  • the balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition.
  • 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.
  • thermally expandable fine particle hollow body described in JP-A No. 2004-51701 or JP-A No. 2004-66749 can be used.
  • a 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.
  • the thermally expandable fine hollow body 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.
  • a silane coupling agent 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.
  • silane coupling agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltris (2-propoxy) silane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyl.
  • Methyldiethoxysilane N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldiethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltriisopropoxysilane, N- ⁇ - ( ⁇ -aminoethyl) aminoethyl- ⁇ -aminopropyltri Methoxysilane, N-6-aminohexyl- ⁇ -amino Propyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, ⁇ -ureidopropyltrime
  • Group-containing silanes ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane , ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane and other epoxy group-containing silanes; ⁇ -carboxyethyltriethoxysilane, ⁇ -carboxyethylphenylbis ( ⁇ -methoxyethoxy) silane, N- ⁇ - ( Carboxysilanes such as carboxymethyl) aminoethyl- ⁇ -aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysi
  • 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.
  • reaction products of various silane coupling agents can 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.
  • 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 relative 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 to 10 parts by weight is particularly preferable.
  • a plasticizer can be added to the composition of the present invention.
  • a plasticizer 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.
  • plasticizer examples 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
  • a polymer plasticizer can be used.
  • 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.
  • the drying property (paintability) when an alkyd paint is applied to the cured product can be improved.
  • polymer plasticizer examples 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 - ⁇ - methyl styrene; group, polyethers such as derivatives obtained by converting the like ether groups polybutadiene, polybutene
  • the amount of the plasticizer used is preferably 5 to 150 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). 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.
  • a solvent or diluent can be added to the composition of the present invention.
  • Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be 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.
  • 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.
  • silicates include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, 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 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 using a conventional method.
  • 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.).
  • the amount used is 0.1 to 20 parts by weight, preferably 100 to 20 parts by weight, preferably 100 parts by weight of the total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.5 to 10 parts by weight.
  • 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 diameter of 10 to 500 ⁇ m 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 100 parts by weight as a total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B).
  • An antioxidant 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.
  • Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); 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 in total of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). 0.2 to 5 parts by weight is preferred.
  • 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 to 5 parts by weight is preferred.
  • 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.
  • 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 stock) 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.).
  • UV absorber can be used in the composition of the present invention.
  • 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.
  • the amount of the ultraviolet absorber 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 to 5 parts by weight is preferred.
  • alkyl alkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Arylalkoxysilanes such as; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, alkylisopropenoxysilane such as ⁇ -glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as
  • 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. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
  • derivatives of alkyl alcohols such as hexanol, octanol, decanol, etc., which produce silicon compounds that produce silane monools such as trimethylsilanol by hydrolysis, and 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 to 5 parts by weight is preferred.
  • 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.
  • 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 terpene resins
  • 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 styrene block copolymer and the hydrogenated product thereof are not particularly limited.
  • styrene-butadiene-styrene block copolymer (SBS) styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS butylene-styrene block copolymer
  • SEPS styrene-ethylenepropylene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • a terpene-phenol resin is preferable because of high compatibility with the polymer (A) and high adhesion effect.
  • a hydrocarbon resin is preferable.
  • the amount of 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 to 30 parts.
  • 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.
  • a compound containing an epoxy group in the composition of the present invention, can be used.
  • the restorability of the cured product can be improved.
  • 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.
  • E-PS epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate.
  • 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).
  • a photocurable material can be used in the composition of the present invention.
  • 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.
  • polyvinyl cinnamates examples include a photosensitive resin having a cinnamoyl group as a photosensitive group, in which polyvinyl alcohol is esterified with cinnamic acid, and many polyvinyl cinnamate derivatives are exemplified.
  • the azide resin is known as a photosensitive resin having an azide group as a photosensitive group.
  • a photosensitive resin in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972).
  • a “photosensitive resin” March 17, 1972.
  • 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, and if it is 20 parts by weight or more, the cured product tends to be too hard and tends to crack.
  • An oxygen curable substance can be used in the composition of the present invention.
  • 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.
  • oxygen curable substance examples 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, 1,3-pentadiene, etc.
  • 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, 1,3-pentadiene, etc.
  • 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
  • various modified products thereof maleinized modified products, boiled oil modified products, etc.
  • drill oil and liquid diene polymers are particularly preferable.
  • the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination.
  • catalysts and metal dryers examples 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.
  • an oxygen curable substance is preferably used in combination with a photocurable substance.
  • a surface property improving agent can be added to the composition of the present invention.
  • surface property improvers include long-chain alkylamines such as laurylamine, 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, tris (2,4-di-tert-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 a total of 100 parts by weight of the reactive silicon group-containing polymer (A) and the reactive silicon group-containing polymer (B). It is preferable to do this.
  • 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 resins include epichlorohydrin-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 Propylene oxide adduct glycidyl ether type epoxy resin, 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
  • 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.
  • 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.
  • 1 to 200 parts by weight of epoxy resin is added to 100 parts by weight of the total 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.
  • composition of the present invention can be used in combination with a curing agent for curing the epoxy resin.
  • a curing agent for curing the epoxy resin.
  • curing agent which can be used
  • curing agent generally used can be used.
  • the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.
  • Ketimine can be used as a curing agent for 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.
  • ketimine 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.
  • amine compounds and carbonyl compounds may be used.
  • 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; polyalkylenepolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; ⁇ -aminopropylto Silane, N-
  • 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 , ⁇ -dicarbonyl
  • the imino group 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.
  • 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.
  • the amount used is the kind of epoxy resin and ketimine It depends on.
  • 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.
  • the composition of the present invention can be used as a foam material using a foaming agent.
  • a liquefied gas such as butane, propane, ethane, methane or dimethyl ether can be used as an aerosol propellant.
  • 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.
  • a siloxane oxyalkylene copolymer can be used as a foam stabilizer.
  • the amount of the blowing 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.
  • 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.
  • the curable composition 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.
  • the curable composition 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.
  • 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.
  • a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration.
  • an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration.
  • lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, ⁇ -
  • an alkoxysilane compound such as glycidoxypropyltrimethoxysilane further improves the storage stability.
  • 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.
  • 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, a curable resin using 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, etc. may be used in combination. it can.
  • 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.
  • 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 edges Liquid seals used in anti-rust / waterproof seals for cutting parts, automobile parts, trucks, buses and other large vehicle parts, train car parts, aircraft parts, marine parts, electrical parts, various machine parts, etc
  • 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.
  • the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
  • Liquid feeding system HLC-8120GPC manufactured by Tosoh Corporation 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 introduction number) [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.
  • allyl chloride was 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.
  • 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and then the water was removed by centrifugation. 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.
  • a polyoxypropylene polymer (Q-1) having an allyl group at the terminal site was obtained.
  • Q-1 a polyoxypropylene polymer having an allyl group at the terminal site
  • 50 ⁇ l of platinum divinyldisiloxane complex solution was added, and 4.8 g of dimethoxymethylsilane was slowly added dropwise with stirring.
  • 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.
  • 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.
  • 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and then the water was removed by centrifugation. 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.
  • 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.
  • 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and then the water was removed by centrifugation. 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.
  • a polyoxypropylene polymer (Q-3) having an allyl group at the terminal site was obtained.
  • Q-3 a polyoxypropylene polymer having an allyl group at the terminal site was obtained.
  • 6.4 g of dimethoxymethylsilane was slowly added dropwise with stirring.
  • 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.
  • polyoxypropylene (Q-4) having a terminal structure having an average of more than 1.0 carbon-carbon unsaturated bond 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.
  • Examples 1 to 4, Comparative Examples 1 to 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 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
  • A-171 product of Momentive: vinyltrimethoxysilane
  • A-1120 product of Momentive: N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane
  • U-220H 1 part by weight of Nitto Kasei Co., Ltd. product: dibutyltin bisacetylacetonate
  • 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 an autograph (AGS-J) manufactured by Shimadzu Corporation at a tension speed of 200 mm / min. The results are shown in Table 1.
  • 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.
  • 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 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, Taipaque R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide), 20 parts by weight, Disparon 6500 (Enomoto) 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-
  • 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 an autograph (AGS-J) manufactured by Shimadzu Corporation at a tension speed of 200 mm / min. The results are shown in Table 2.
  • 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.
  • 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 Ci
  • A-171 (Mentive: vinyltrimethoxysilane)
  • A-1120 (Mentive: N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane)
  • 1-phenylguanidine After adding 0.55 parts by weight of 45% Nn-butylbenzenesulfonamide solution (Nippon Carbide Co., Ltd .: PhG / BBSA) and mixing well with a spatula, the mixture was uniformly mixed and defoamed using a rotating and rotating mixer. .
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

L'objet de la présente invention est de fournir une composition durcissable présentant des propriétés améliorées d'aptitude au durcissement, de vitesse de restauration, de résistance aux intempéries et de résistance au déchirement, et un produit durci obtenu à partir de ladite composition durcissable. Cette composition durcissable est un mélange d'un polymère (A) contenant un groupe silicium réactif comprenant en moyenne 1,0 ou quelques groupes silicium réactifs sur une extrémité terminale, et d'un polymère (B) contenant un groupe silicium réactif comprenant en moyenne plus de 1,0 groupe silicium réactif sur une extrémité terminale. De préférence, la chaîne principale du polymère (A) et/ou (B) contenant un groupe silicium réactif est un polymère polyoxyalkylène, et de préférence, le polymère (B) contenant un groupe silicium réactif comprend en moyenne plus de 1,5 groupes silicium réactifs sur une extrémité terminale.
PCT/JP2014/081000 2013-11-29 2014-11-25 Composition durcissable WO2015080067A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015105323A (ja) * 2013-11-29 2015-06-08 株式会社カネカ 硬化性組成物
EP3409730A4 (fr) * 2016-02-08 2019-01-16 Kaneka Corporation Composition durcissable présentant une adhésivité améliorée résistante à l'eau
WO2019159972A1 (fr) * 2018-02-13 2019-08-22 株式会社カネカ Composition durcissable à composant unique pour joint de travail
JP2019156885A (ja) * 2018-03-07 2019-09-19 Ａｇｃ株式会社 硬化性組成物、及び硬化物
JP2019189863A (ja) * 2018-04-20 2019-10-31 Ａｇｃ株式会社 硬化性組成物及び硬化物
JP2020041158A (ja) * 2018-05-07 2020-03-19 Ａｇｃ株式会社 硬化性組成物及び硬化物
CN113166395A (zh) * 2018-11-27 2021-07-23 株式会社钟化 聚氧化烯系聚合物及固化性组合物
WO2022163563A1 (fr) * 2021-01-29 2022-08-04 株式会社カネカ Polymère à base de polyoxyalkylène et mélange de celui-ci
WO2023054701A1 (fr) * 2021-10-01 2023-04-06 株式会社カネカ Composition durcissable
WO2023127443A1 (fr) * 2021-12-27 2023-07-06 株式会社カネカ Composition durcissable et produit durci de celle-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272733A (ja) * 2004-03-25 2005-10-06 Kaneka Corp 新規な官能基含有ポリオキシアルキレン系重合体及び製造方法
WO2012057092A1 (fr) * 2010-10-27 2012-05-03 株式会社カネカ Composition durcissable
WO2013180203A1 (fr) * 2012-05-31 2013-12-05 株式会社カネカ Polymère présentant une structure terminale comprenant une pluralité de groupes réactifs de silicium, son procédé de fabrication et son utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272733A (ja) * 2004-03-25 2005-10-06 Kaneka Corp 新規な官能基含有ポリオキシアルキレン系重合体及び製造方法
WO2012057092A1 (fr) * 2010-10-27 2012-05-03 株式会社カネカ Composition durcissable
WO2013180203A1 (fr) * 2012-05-31 2013-12-05 株式会社カネカ Polymère présentant une structure terminale comprenant une pluralité de groupes réactifs de silicium, son procédé de fabrication et son utilisation

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015105323A (ja) * 2013-11-29 2015-06-08 株式会社カネカ 硬化性組成物
EP3409730A4 (fr) * 2016-02-08 2019-01-16 Kaneka Corporation Composition durcissable présentant une adhésivité améliorée résistante à l'eau
WO2019159972A1 (fr) * 2018-02-13 2019-08-22 株式会社カネカ Composition durcissable à composant unique pour joint de travail
JP2019156885A (ja) * 2018-03-07 2019-09-19 Ａｇｃ株式会社 硬化性組成物、及び硬化物
JP7342412B2 (ja) 2018-04-20 2023-09-12 Ａｇｃ株式会社 硬化性組成物及び硬化物
JP2019189863A (ja) * 2018-04-20 2019-10-31 Ａｇｃ株式会社 硬化性組成物及び硬化物
JP2020041158A (ja) * 2018-05-07 2020-03-19 Ａｇｃ株式会社 硬化性組成物及び硬化物
CN113166395A (zh) * 2018-11-27 2021-07-23 株式会社钟化 聚氧化烯系聚合物及固化性组合物
EP3889206A4 (fr) * 2018-11-27 2022-08-24 Kaneka Corporation Polymère de polyoxyalkylène et composition durcissable
JP7394783B2 (ja) 2018-11-27 2023-12-08 株式会社カネカ ポリオキシアルキレン系重合体を含む硬化性組成物
CN113166395B (zh) * 2018-11-27 2024-01-05 株式会社钟化 聚氧化烯系聚合物及固化性组合物
WO2022163563A1 (fr) * 2021-01-29 2022-08-04 株式会社カネカ Polymère à base de polyoxyalkylène et mélange de celui-ci
WO2023054701A1 (fr) * 2021-10-01 2023-04-06 株式会社カネカ Composition durcissable
WO2023127443A1 (fr) * 2021-12-27 2023-07-06 株式会社カネカ Composition durcissable et produit durci de celle-ci

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