WO2023054701A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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WO2023054701A1
WO2023054701A1 PCT/JP2022/036817 JP2022036817W WO2023054701A1 WO 2023054701 A1 WO2023054701 A1 WO 2023054701A1 JP 2022036817 W JP2022036817 W JP 2022036817W WO 2023054701 A1 WO2023054701 A1 WO 2023054701A1
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group
reactive silicon
polymer
groups
weight
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PCT/JP2022/036817
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Japanese (ja)
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寛 安藤
新太郎 幸光
リュック ピータース，
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株式会社カネカ
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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • 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
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a curable composition containing a reactive silicon group-containing polyoxyalkylene polymer.
  • Polymers with reactive silicon groups are known as moisture-reactive polymers, are included in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and are used in a wide range of fields. there is
  • Polymer components of such reactive silicon group-containing polymers include various polymers such as polyoxyalkylene-based polymers, saturated hydrocarbon-based polymers, and (meth)acrylic acid ester-based copolymers.
  • polyoxyalkylene polymers have relatively low viscosity at room temperature and are easy to handle, and the cured product obtained after the reaction exhibits good elasticity.
  • Tin catalysts are often used as curing catalysts, but there are cases where catalysts other than tin catalysts are required.
  • a titanium catalyst has been developed as one of the catalysts other than tin (see Patent Documents 1 and 2).
  • An object of the present invention is to provide a curable composition with improved breaking strength and breaking elongation after curing without using a tin catalyst.
  • the inventors of the present invention completed the following invention as a result of intensive studies to solve the above problems.
  • the present invention has a reactive silicon group of general formula (1), a terminal structure has the reactive silicon group, a terminal olefin group and/or an internal olefin group, and the Containing a reactive silicon group-containing polyoxyalkylene polymer (A) in which the total number of reactive silicon groups, the terminal olefin groups and the internal olefin groups is more than 1.0 on average per terminal structure death, —Si(R 1 ) 3-a X a (1)
  • R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
  • Each X is independently a hydroxyl group or a hydrolyzable group.
  • a is 1, 2, or 3.
  • a titanium compound (B) represented by general formula (2), and (R 2 —O) n Ti—A 4-n (2) (R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; A is a ⁇ -diketone group.) It relates to a curable composition containing ammonium hydroxide (C) or containing a reaction product of said titanium compound (B) and said ammonium hydroxide (C).
  • the present invention can provide a curable composition with improved breaking strength and breaking elongation after curing without using a tin catalyst.
  • the curable composition according to the present disclosure contains a polyoxyalkylene polymer (A) having a reactive silicon group represented by general formula (1) (hereinafter also referred to as polymer (A)).
  • the terminal structure of the polymer (A) has the reactive silicon group, the terminal olefin group and/or the internal olefin group, and the reactive silicon group, the terminal olefin group and the internal olefin group in the terminal structure
  • the total number of groups is on average greater than 1.0 per said terminal structure.
  • the reactive silicon group-containing polyoxyalkylene-based polymer (A) has a polymer skeleton composed of repeating units of oxyalkylene and a terminal structure bonded to the end of the polymer skeleton.
  • the polymer skeleton of the reactive silicon group-containing polyoxyalkylene-based polymer (A) may be linear or branched.
  • the skeleton is preferable in that the cured product of the curable composition has high elongation and high tear strength.
  • a linear polymer backbone can be formed by using an initiator with two hydroxyl groups per molecule in the polymerization process to form the polymer backbone, and a branched polymer backbone can be formed by: It can be formed by using an initiator having 3 or more hydroxyl groups in one molecule.
  • terminal structure refers to a site that does not contain a repeating unit that constitutes the polymer backbone and that is bonded to the end of the polymer backbone.
  • the polymer skeleton is linear, one or two terminal structures are present per polymer molecule, and when the polymer skeleton is branched, three or more terminal structures are present per polymer molecule. do.
  • the polymer backbone is a mixture of linear and branched chains, the average number of terminal structures per polymer molecule can be between 2 and 3.
  • the terminal structure is preferably bonded to an oxyalkylene unit positioned at the end of the polymer skeleton via an oxygen atom.
  • the reactive silicon group possessed by the reactive silicon group-containing polyoxyalkylene polymer (A) is preferably contained in the terminal structure.
  • each terminal structure may contain a reactive silicon group, or a terminal structure containing a reactive silicon group and a terminal structure not containing a reactive silicon group may coexist.
  • the reactive silicon group-containing polyoxyalkylene polymer (A) has a terminal structure having a reactive silicon group and either one or both of a terminal olefin group and an internal olefin group.
  • a terminal structure having a reactive silicon group and a terminal olefin group and/or an internal olefin group means that all the individual terminal structures contained in the polymer have a reactive silicon group, a terminal olefin group and/or an internal olefin group. group, and the terminal structure has a reactive silicon group and a terminal olefin group and/or an internal olefin group in the totality of the polymer (A) containing a large number of polymer molecules.
  • the terminal structure in one molecule contained in the polymer (A) may have only a reactive silicon group and not have a terminal olefin group or an internal olefin group, or may have a terminal olefin It may have either one or both of groups and internal olefin groups, but may not have reactive silicon groups.
  • the total number of reactive silicon groups, terminal olefin groups and internal olefin groups in the terminal structure is 1.0 on average per terminal structure. is more than. In this way, by using a reactive silicon group-containing polyoxyalkylene polymer having a large total number of specific groups per terminal structure in combination with a curing catalyst described later, the breaking strength and breaking elongation after curing are improved. be able to.
  • the total number is preferably 1.2 or more, more preferably 1.4 or more.
  • the upper limit of the total number is not particularly limited, it is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less.
  • the average number of reactive silicon groups per terminal structure of the reactive silicon group-containing polyoxyalkylene polymer (A) is preferably 0.5 or more, preferably 0.8 or more. It is more preferably 1.0 or more, and most preferably 1.2 or more.
  • the upper limit of the number of reactive silicon groups per terminal structure of the polymer (A) is not particularly limited, but is preferably 4.0 or less, more preferably 3.0 or less, 2.0 or less is particularly preferred.
  • the average number of reactive silicon groups contained in one molecule of the reactive silicon group-containing polyoxyalkylene polymer (A) is preferably 0.5 to 8.0, more preferably 1.0 to 6.0. It is more preferably 0, more preferably 1.5 to 5.0.
  • the reactive silicon group-containing polyoxyalkylene polymer (A) has the general formula (1): —Si(R 1 ) 3-a X a (1)
  • R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
  • X each independently represents a hydroxyl group or a hydrolyzable represents a group, and a is 1, 2, or 3.
  • It has a reactive silicon group represented by
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms.
  • the number of carbon atoms in the hydrocarbon group for R 1 is preferably 1-12, more preferably 1-6, and particularly preferably 1-4.
  • the hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.
  • the hetero-containing group which the hydrocarbon group as R 1 may have as a substituent is a group containing a hetero atom.
  • atoms other than carbon atoms and hydrogen atoms are heteroatoms.
  • heteroatoms include N, O, S, P, Si, and halogen atoms.
  • the total number of carbon atoms and heteroatoms is preferably 1-10, more preferably 1-6, even more preferably 1-4.
  • mercapto groups halogen atoms such as Cl, Br, I, and F; nitro groups; cyano groups; methoxy, ethoxy, n-propyloxy, and isopropyloxy groups.
  • alkoxy groups such as; alkylthio groups such as methylthio, ethylthio, n-propylthio, and isopropylthio; acyl groups such as acetyl, propionyl, and butanoyl; acetyloxy, propionyloxy, and butanoyl.
  • Acyloxy group such as oxy group; substituted or unsubstituted amino group such as amino group, methylamino group, ethylamino group, dimethylamino group and diethylamino group; aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, dimethyl substituted or unsubstituted aminocarbonyl groups such as an aminocarbonyl group and a diethylaminocarbonyl group; and a cyano group.
  • R 1 is a hydrocarbon group substituted with a hetero-containing group
  • the total number of carbon atoms and hetero atoms in R 1 is preferably from 2 to 30, more preferably from 2 to 18, and further from 2 to 10. 2 to 6 are particularly preferred.
  • hydrocarbon groups having 1 to 20 carbon atoms as R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl.
  • n-pentyl group n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; vinyl group, 2-propenyl group, 3 alkenyl groups such as -butenyl group and 4-pentenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-
  • R 1 include alkyl groups such as methyl group and ethyl group; alkyl groups having hetero-containing groups such as chloromethyl group and methoxymethyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as; aralkyl groups such as benzyl group; and the like.
  • R 1 is preferably a methyl group, a methoxymethyl group and a chloromethyl group, more preferably a methyl group and a methoxymethyl group, and still more preferably a methyl group.
  • Examples of X include hydroxyl group, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group.
  • an alkoxy group is more preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable, since they are moderately hydrolyzable and easy to handle.
  • a is 1, 2, or 3; As a, 2 or 3 is preferable, and 3 is more preferable because curability is improved and high strength is obtained.
  • reactive silicon groups include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group and a dimethoxyethylsilyl group.
  • trimethoxysilyl group a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because it improves curability.
  • the internal olefin group refers to a carbon-carbon double bond that does not have a methylidene group, and is a group that can be generated by, for example, a transfer reaction of the terminal olefin group during production of the polymer (A).
  • Specific examples include a 1-propenyl group and the like.
  • a typical example of the terminal structure is the terminal structure represented by the following general formula (3).
  • the general formula (3) shows a terminal structure having a reactive silicon group but not having a terminal olefin group and an internal olefin group.
  • R 1 , X and a are the same as above.
  • R 3 and R 5 are each independently a divalent C 1-6 linking group which may contain a heteroatom.
  • R 4 and R 6 are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
  • n is an integer of 1-10.
  • R 3 is a divalent C 1-6 bonding group which may contain a heteroatom, and the bonding group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. .
  • the number of carbon atoms is preferably 1-4, more preferably 1-3, even more preferably 1-2.
  • CH 2 OCH 2 , CH 2 O and CH 2 are preferred, and CH 2 OCH 2 is more preferred.
  • R 4 is preferably hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and hydrogen or 1 to 2 carbon atoms. is more preferred.
  • a hydrogen atom and a methyl group are particularly preferred, and a hydrogen atom is most preferred.
  • R 5 is a divalent C 1-6 bonding group which may contain a heteroatom, and the bonding group is preferably a hydrocarbon group or a hydrocarbon group containing a heteroatom. , a hydrocarbon group having 1 to 2 carbon atoms is more preferred.
  • the heteroatoms are preferably oxygen atoms and/or nitrogen atoms.
  • the bonding group is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or C(O)NH 2 CH 2 , and particularly preferably a methylene group.
  • R 6 is preferably hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and hydrogen or 1 to 2 carbon atoms. is more preferred.
  • a hydrogen atom and a methyl group are particularly preferred, and a hydrogen atom is most preferred.
  • the terminal structure represented by general formula (3) represents one terminal structure bonded to one terminal of the polymer skeleton. Although two or more reactive silicon groups are shown in formula (3), formula (3) does not indicate two or more terminals, but rather two or more reactive silicon groups in one terminal structure. This indicates the presence of silicon groups. Moreover, except for oxygen on the left end, the formula (3) does not include a polymer skeleton composed of repeating units such as oxyalkylene units. In other words, n structures in parentheses in formula (3) do not correspond to repeating units in the polymer skeleton.
  • the main chain structure of the reactive silicon group-containing polyoxyalkylene polymer (A) may be linear or branched, but is preferably linear.
  • the main chain of the reactive silicon group-containing polyoxyalkylene polymer (A) is represented by —R 7 —O— (wherein R 7 is a linear or branched alkylene group having 1 to 14 carbon atoms). R 7 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -R 7 -O- include -CH 2 O-, -CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, and -CH 2 C(CH 3 ).
  • the number average molecular weight of the reactive silicon group-containing polyoxyalkylene polymer (A) is not particularly limited, but the polystyrene equivalent molecular weight in GPC is preferably 5,000 to 100,000, and 10,000 to 40,000. More preferably, 12,000 to 25,000 is particularly preferred, and 13,000 to 20,000 is most preferred.
  • the introduction amount of the reactive silicon group is moderate, so that the production cost is kept within a moderate range, and the reactive silicon group-containing polyoxyalkylene polymer having high strength is obtained. Coalescence (A) is easily obtained.
  • the polymer precursor before introduction of the reactive silicon group was measured by the hydroxyl value measurement method of JIS K 1557 and Terminal group equivalent molecular weight obtained by directly measuring the terminal group concentration by titration analysis based on the principle of the iodine value measurement method and considering the polymer structure (branching degree determined by the polymerization initiator used) can also be shown as
  • the terminal group-equivalent molecular weight of the polymer (A) is obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned terminal group-equivalent molecular weight, and performing GPC of the reactive silicon group-containing polymer. It is also possible to obtain by converting the number average molecular weight obtained by the method into a terminal group equivalent molecular weight.
  • the molecular weight distribution (Mw/Mn) of the reactive silicon group-containing polyoxyalkylene polymer (A) is not particularly limited, it is preferably narrow. Specifically, it is preferably 1.6 or less, more preferably 1.4 or less, still more preferably 1.3 or less, and particularly preferably 1.2 or less.
  • the molecular weight distribution of the reactive silicon group-containing polyoxyalkylene polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
  • the reactive silicon group-containing polyoxyalkylene polymer (A) is obtained by introducing an olefin group into the hydroxyl-terminated polyoxyalkylene polymer (a1) by utilizing the reactivity of the hydroxyl group, and then combining with the olefin group.
  • a method of introducing a reactive silicon group by reacting a reactive silicon group-containing compound having reactivity is preferred.
  • the polymer skeleton of the polyoxyalkylene-based polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, whereby a hydroxyl-terminated polyoxyalkylene-based polymer (a1) is obtained. is obtained.
  • a hydroxyl-terminated polyoxyalkylene-based polymer (a1) is obtained.
  • Mw/Mn small molecular weight distribution
  • a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is used. is preferred.
  • hydroxyl-containing initiators include, but are not limited to, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, methanol, ethanol, propanol, Examples include organic compounds having one or more hydroxyl groups, such as butanol, pentanol, hexanol, low-molecular-weight polyoxypropylene monoallyl ether, and low-molecular-weight polyoxypropylene monoalkyl ether.
  • the epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.
  • reaction with alkali metal salt In introducing an olefin group into the hydroxyl group-terminated polyoxyalkylene polymer (a1), first, an alkali metal salt is allowed to act on the hydroxyl group-terminated polyoxyalkylene polymer (a1) to convert the terminal hydroxyl group to a metaloxy group. is preferably converted to A double metal cyanide complex catalyst can also be used instead of the alkali metal salt. As described above, the metaloxy group-terminated polyoxyalkylene polymer (a2) is formed.
  • the alkali metal salt is not particularly limited, examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
  • Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred.
  • the alkali metal salt may be dissolved in a solvent before being subjected to the reaction.
  • the amount of the alkali metal salt to be used is not particularly limited. 7 or more is more preferable, and 0.8 or more is even more preferable.
  • the molar ratio is preferably 1.2 or less, more preferably 1.1 or less.
  • the temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 145°C or lower.
  • the time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.
  • reaction with electrophile (a3) By reacting the metaloxy group-terminated polyoxyalkylene polymer (a2) obtained as described above with an electrophilic agent (a3) having an olefin group, the metaloxy group is converted to a structure containing an olefin group can be converted to As a result, a polyoxyalkylene polymer (a4) having an olefin group in the terminal structure is formed.
  • the electrophilic agent (a3) having an olefin group is particularly limited as long as it is a compound capable of reacting with the metaloxy group possessed by the polyoxyalkylene polymer (a2) and introducing an olefin group into the polyoxyalkylene polymer.
  • Examples include an epoxy compound (a3-1) having an olefin group and an organic halide (a3-2) having an olefin group.
  • the epoxy compound (a3-1) having an olefin group which is one embodiment of the electrophile (a3), reacts with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond to form a poly
  • a structure containing an olefin group and a hydroxyl group can be introduced as the terminal structure of the oxyalkylene polymer.
  • one or more epoxy compounds (a3- 1) can be added.
  • the epoxy compound (a3-1) having an olefin group is, but not limited to, the following general formula (4):
  • R 3 and R 4 are the same groups as R 3 and R 4 described above for general formula (3), respectively.
  • epoxy compound (a3-1) having an olefin group are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and butadiene monoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl Ethers are particularly preferred.
  • the amount of the epoxy compound (a3-1) having an olefin group to be added can be any amount in consideration of the introduction amount and reactivity of the olefin group to the polymer.
  • the molar ratio of the epoxy compound (a3-1) to the hydroxyl groups of the polyoxyalkylene polymer (a1) is preferably 0.2 or more, more preferably 0.5 or more.
  • the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
  • the reaction temperature for the ring-opening addition reaction of the epoxy compound (a3-1) having an olefin group to the metaloxy group-terminated polyoxyalkylene polymer (a2) is 60° C. or higher and 160° C. or lower. , and more preferably 110°C or higher and 150°C or lower.
  • the epoxy compound (a3-1) having an olefin group is allowed to act on the metaloxy group-terminated polyoxyalkylene polymer (a2), a new metaloxy group is generated by ring-opening of the epoxy group. Therefore, after the epoxy compound (a3-1) is allowed to act, the organic halide having an olefin group (a3-2) can be allowed to act continuously. This method is preferable because the amount of olefin groups introduced into the polymer and the amount of reactive silicon groups introduced can be increased.
  • the organic halide (a3-2) having an olefin group reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, and has a structure containing an olefin group as a terminal structure of the polyoxyalkylene polymer.
  • organic halide having an olefin group (a3-2) are not particularly limited, but vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, and propargyl bromide. , vinyl iodide, allyl iodide, methallyl iodide, propargyl iodide and the like. Allyl chloride and methallyl chloride are preferred for ease of handling.
  • the addition amount of the organic halide (a3-2) having an olefin group is not particularly limited, but the molar ratio of the organic halide (a3-2) to the hydroxyl group of the polyoxyalkylene polymer (a1) is 0. 0.7 or more is preferable, and 1.0 or more is more preferable. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
  • the temperature at which the metaloxy group-terminated polyoxyalkylene polymer (a2) is reacted with the organic halide (a3-2) having an olefin group is preferably 50° C. or higher and 150° C. or lower, and 110° C. or higher and 140° C. °C or less is more preferable.
  • the reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.
  • the terminal structure represented by the general formula (3) can be formed by introducing a reactive silicon group as described below.
  • the polyoxyalkylene polymer (a4) having an olefin group in the terminal structure obtained above is subjected to a hydrosilylation reaction with a hydrosilane compound (a5) having a reactive silicon group to give the polymer a reactive silicon groups can be introduced.
  • a reactive silicon group-containing polyoxyalkylene polymer (A) having a polyoxyalkylene polymer main chain is produced.
  • the hydrosilylation reaction has the advantage that it can be easily carried out, the introduction amount of the reactive silicon group can be easily adjusted, and the physical properties of the obtained polymer are stable.
  • hydrosilane compound (a5) having a reactive silicon group include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl) ) chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane and other halosilanes; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyl dimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane,
  • the amount of the hydrosilane compound (a5) having a reactive silicon group to be used may be appropriately set in consideration of the amount of olefin groups possessed by the polyoxyalkylene polymer (a4).
  • the molar ratio of the hydrosilane compound (a5) to the olefin group of the polyoxyalkylene polymer (a4) is preferably 0.05 or more and 10 or less, more preferably 0.3 or more and 3 or less, from the viewpoint of reactivity. more preferred.
  • the molar ratio is more preferably 0.5 or more, particularly preferably 0.7 or more, in that the modulus value of the cured product can be increased.
  • the molar ratio is more preferably 2.5 or less, and particularly preferably 2 or less.
  • the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction.
  • a hydrosilylation catalyst metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, and complexes thereof are known, and these can be used.
  • platinum-phosphine complexes [eg Ph(PPh 3 ) 4 , Pt(PBu 3 ) 4 ]; platinum-phosphite complexes [eg Pt ⁇ P(OPh) 3 ⁇ 4 ]; be done.
  • platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.
  • the temperature conditions for the hydrosilylation reaction are not particularly limited and can be appropriately set by those skilled in the art. However, in order to reduce the viscosity of the reaction system and improve the reactivity, the reaction is preferably performed under heating conditions. , the reaction at 50°C to 150°C is more preferred, and the reaction at 70°C to 120°C is even more preferred.
  • the reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.
  • a curable composition according to an aspect of the present disclosure can contain a titanium compound (B) represented by general formula (2).
  • (R 2 —O) n Ti—A 4-n (2) R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; A is a ⁇ -diketone group
  • the substituted or unsubstituted hydrocarbon group represented by R 2 is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, more preferably an aliphatic hydrocarbon group.
  • Aliphatic hydrocarbon groups include saturated or unsaturated hydrocarbon groups. A linear or branched alkyl group is preferred as the saturated hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is 1-10, preferably 1-6, more preferably 1-4.
  • Hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl.
  • Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, an acetoxy group, and the like. When there are multiple R2 's, they may be the same or different.
  • the ⁇ -diketone group represented by A is not particularly limited as long as it is a ⁇ -diketone group that can be blended with titanium.
  • 1-aryl-1,3-butanedione such as ,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, 1-(4-methoxyphenyl)-1,3-butanedione , 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, 1,3-bis(4-methoxyphenyl)-1,3-propanedione diketones such as 1,3-diaryl-1,3-propanedione such as 3-benzyl-2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl
  • malonic acid esters and malonic acid amides such as N,N,N',N'-tetramethylmalonamide and N,N,N',N'-tetraethylmalonamide.
  • diketones and ketoamides are preferred, and diketones are more preferred.
  • 2,4-pentanedione, 1-aryl-1,3-butanedione, 1,3-diaryl-1,3-propanedione, methylacetoacetate and ethylacetoacetate are preferred, and methylacetoacetate and ethylacetoacetate are preferred.
  • Acetate is particularly preferred. When there are multiple A's, they may be the same or different.
  • n represents an integer of 1 to 4. n preferably represents 2, 3 or 4, particularly preferably 4, so that better curability can be achieved.
  • titanium compound represented by the general formula (2) examples include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxy Dibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytri isopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxyd
  • the above titanium compound (B) may be used alone or in combination of two or more.
  • the amount of the titanium compound (B) used is, when the titanium compound (B) and the ammonium hydroxide (C) are used without being reacted in advance, relative to 100 parts by weight of the polymer (A) having a reactive silicon group. 0.1 to 20 parts by weight is preferable, 0.5 to 10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable.
  • a curable composition according to one aspect of the present disclosure may comprise ammonium hydroxide (C).
  • Ammonium hydroxide (C) is preferably represented by the following general formula (6).
  • R 8 , R 9 , R 10 and R 11 are the same or different and represent a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms.
  • Y represents a hydroxyl group.
  • the substituted or unsubstituted hydrocarbon group represented by R 8 , R 9 , R 10 and R 11 is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is more preferred.
  • a linear or branched alkyl group is preferable as the aliphatic hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is 1-8, preferably 1-6, more preferably 1-4.
  • aliphatic hydrocarbon groups include saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group and octyl group; group, allyl group, prenyl group, crotyl group, cyclopentadienyl group, and other unsaturated hydrocarbon groups, preferably methyl group, ethyl group, and butyl group.
  • saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group and octyl group
  • aromatic hydrocarbon group examples include phenyl group, tolyl group, and benzyl group.
  • Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxy group, and an acetoxy group.
  • Examples of substituted hydrocarbon groups include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group and ethoxyethyl group; hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group and 3-hydroxypropyl group; 2-acetoxyethyl group and the like.
  • ammonium hydroxide represented by the general formula (6) examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide, trimethylbenzyl ammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide and the like.
  • tetraalkylammonium hydroxide is preferred, and tetrabutylammonium hydroxide is preferred.
  • ammonium hydroxide (C) when the titanium compound (B) and the ammonium hydroxide (C) are used without being reacted in advance, 100 parts by weight of the polymer (A) having a reactive silicon group On the other hand, 0.1 to 20 parts by weight is preferable, 0.5 to 10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable.
  • the content ratio (B/C) of the titanium compound (B) and the ammonium hydroxide (C) is in the range of 0.1/1 to 10/1 in terms of molar ratio, from the viewpoint of obtaining good curability. is preferably from 1/1 to 10/1, more preferably from 2/1 to 5/1.
  • the curable composition according to the present disclosure may contain the titanium compound (B) and the ammonium hydroxide (C), respectively, or may react the titanium compound (B) and the ammonium hydroxide (C). It may contain a reaction product obtained by the reaction. In either embodiment, the breaking strength and breaking elongation after curing can be improved, but from the viewpoint of improving the strength and elongation, the embodiment using the reaction product is preferable.
  • the reaction product can be obtained by reacting a mixture of both at, for example, 40 to 100°C. Specifically, this temperature is preferably 40 to 100°C.
  • the molar ratio of titanium compound (B) to ammonium hydroxide (C) in the mixture may be, for example, 0.1-100, more preferably 0.2-10.
  • the amount of the reaction product of the titanium compound (B) and ammonium hydroxide (C) used is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer (A) having a reactive silicon group. , more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.
  • the curable composition according to the present disclosure may further contain a (meth)acrylate polymer (D) having a reactive silicon group (hereinafter also referred to as polymer (D)). Weather resistance and adhesiveness can be improved by containing the polymer (D).
  • the (meth)acrylic acid ester-based monomer constituting the main chain of the (meth)acrylic acid ester-based polymer (D) having a reactive silicon group is not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
  • tert-butyl (meth)acrylate n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate , glycidyl (meth)acrylate, (3
  • Examples of monomer units other than the above include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as N-methylol acrylamide and N-methylol methacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; , diethylaminoethyl methacrylate, and the like.
  • the (meth)acrylate polymer (D) may be a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith.
  • the vinyl-based monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like.
  • Fluorine-containing vinyl monomers Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyl esters; Fumaric acid, fumaric acid monoalkyl esters and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Containing vinyl-based monomers; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl
  • a copolymer composed of a styrene monomer and a (meth)acrylic acid monomer is preferable because of its excellent physical properties.
  • a (meth)acrylic ester-based polymer composed of an acid ester monomer is more preferable, and an acrylic ester-based polymer composed of an acrylic ester monomer is particularly preferable.
  • the average number of reactive silicon groups in the polymer (D) is preferably 1.0 to 5.0 per molecule, and from the viewpoint of mechanical properties during curing of the curable composition, 1.27 or more. is more preferable, and from the viewpoint of the stability of the polymer (D), 3.0 or less is more preferable.
  • the method for introducing a reactive silicon group into the (meth)acrylic acid ester polymer is not particularly limited, and for example, the following method can be used.
  • V group a reactive functional group
  • a method of reacting the hydroxyl group with an isocyanate silane having a reactive silicon-containing group, or after copolymerizing glycidyl acrylate, the epoxy group and the reactive Examples include a method of reacting an aminosilane compound having a silicon-containing group.
  • Examples of the silicon compound that can be used to introduce the reactive silicon group of the (meth)acrylic acid ester polymer (D) using the above method include the following compounds.
  • Compounds having a polymerizable unsaturated group and a reactive silicon group used in method (i) include 3-(trimethoxysilyl)propyl (meth)acrylate and 3-(dimethoxymethylsilyl)propyl (meth)acrylate.
  • trimethoxysilylpropyl (meth)acrylate and (dimethoxymethylsilyl)propyl (meth)acrylate are particularly preferred.
  • Mercaptosilane compounds with reactive silicon-containing groups used in method (ii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, mercaptomethyltriethoxysilane and the like.
  • Compounds having a reactive silicon group and a functional group reactive with the V group used in method (iii) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanate isocyanatosilane compounds such as methyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 - epoxysilane compounds such as glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, glycid
  • the reactive silicon group of polymer (D) has the general formula (7): —SiR 12 3-b Z b (7)
  • R 12 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
  • Z each independently represents a hydroxyl group or a hydrolyzable represents a group, and b is 1, 2, or 3.
  • b is 1, 2, or 3.
  • R 12 is a hydrocarbon group having 1 to 20 carbon atoms.
  • the number of carbon atoms in the hydrocarbon group for R 12 is preferably 1-12, more preferably 1-6, and particularly preferably 1-4.
  • the hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.
  • R 12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n - alkyl groups such as pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups; alkenyl groups such as vinyl, 2-propenyl, 3-butenyl groups,
  • R 12 examples include, for example, alkyl groups such as methyl group and ethyl group; alkyl groups having hetero-containing groups such as chloromethyl group and methoxymethyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as; aralkyl groups such as benzyl group; and the like.
  • R 12 is preferably a methyl group, a methoxymethyl group and a chloromethyl group, more preferably a methyl group and a methoxymethyl group, and still more preferably a methyl group.
  • Z examples include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
  • alkoxy groups such as methoxy and ethoxy are more preferable, methoxy and ethoxy are more preferable, and methoxy is particularly preferable, because they are moderately hydrolyzable and easy to handle.
  • b is 1, 2, or 3; b is preferably 2 or 3.
  • reactive silicon groups include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group and a dimethoxyethylsilyl group.
  • the number average molecular weight of the polymer (D) is not particularly limited, but the polystyrene equivalent molecular weight measured by GPC is preferably 500 to 100,000, more preferably 500 to 50,000, and particularly preferably 1,000 to 30,000. .
  • the method of blending the polymer (A) and the polymer (D) having a reactive silicon group is disclosed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11- No. 116763, etc., have proposed this.
  • a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can be used. This manufacturing method is specifically disclosed in each publication such as JP-A-59-78223, JP-A-60-228516 and JP-A-60-228517.
  • Polymer (A) and polymer (D) can also be blended by similar methods, but are not limited thereto.
  • the mixing ratio of polymer (A) and polymer (D) is not particularly limited, but (A):(D) is preferably 95:5 to 5:95 (parts by weight), and 80:20 to 20:80 (parts by weight). Parts by weight) is more preferred, and 70:30 to 30:70 (parts by weight) is particularly preferred.
  • the polymer (A) and the polymer (D) may be used alone or in combination of two or more.
  • the curable composition according to the present disclosure includes additives such as other silanol condensation catalysts and fillers. , Adhesion imparting agents, plasticizers, solvents, diluents, anti-sagging agents, antioxidants, light stabilizers, ultraviolet absorbers, physical property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, Oxygen-curable substances, epoxy resins, and other resins may be added.
  • additives may be added to the curable composition according to the present disclosure as necessary for the purpose of adjusting various physical properties of the curable composition or cured product.
  • additives examples include surface property modifiers, foaming agents, curability modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxides, Examples include decomposing agents, lubricants, pigments, and antifungal agents.
  • silanol condensation catalyst for hydrolyzing and condensing the reactive silicon groups of the polymer (A) having reactive silicon groups, a titanium compound (B) and ammonium hydroxide (C), or reaction products thereof is used, but other silanol condensation catalysts may also be used.
  • silanol condensation catalysts include, for example, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.
  • organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), phosphate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reaction products of dibutyltin oxide and silicate compounds, reaction products of dioctyltin oxide and silicate compounds, dibutyltin oxide and phthalates and the like.
  • carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
  • carboxylic acid group the following carboxylic acid and various metals can be combined.
  • iron 2-ethylhexanoate (bivalent), iron 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent), vanadium 2-ethylhexanoate (3 valence), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), barium 2-ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent) , Nickel 2-ethylhexanoate (divalent), Cobalt 2-ethylhexanoate (divalent), Zirconium 2-ethylhexanoate (tetravalent), Iron neodecanoate (divalent), Iron neodecanoate (3 valence), titanium neodecanoate (tetravalent), vanadium neodecanoate (trivalent), calcium neo
  • amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine compounds;
  • carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
  • alkoxy metals include aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).
  • fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
  • Two or more different silanol condensation catalysts may be used in combination.
  • the amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, relative to 100 parts by weight of the polymer (A) having a reactive silicon group. 0.01 to 10 parts by weight are particularly preferred.
  • Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.
  • the amount of filler used is preferably 1 to 600 parts by weight, particularly preferably 50 to 400 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.
  • the balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.
  • the amount of the balloon used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • Adhesion imparting agents can be added to the curable composition according to the present disclosure.
  • a silane coupling agent or a reactant of the silane coupling agent can be added as an adhesion imparting agent.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
  • Condensates of various silane coupling agents such as condensates of aminosilane, condensates of aminosilane and other alkoxysilanes; reaction products of aminosilane and epoxysilane; reaction products of aminosilane and (meth)acrylic group-containing silane; A reaction product of various silane coupling agents such as can also be used.
  • Specific examples include Dynasylan 1146 and Dynasylan 1124 (manufactured by EVONIK).
  • the adhesiveness-imparting agent may be used alone or in combination of two or more.
  • the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • plasticizer can be added to the curable composition according to the present disclosure.
  • plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, trade name: Hexamoll DINCH (manufactured by BASF)); Aliphatic polyvalent carboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate and tributyl ace
  • polymer plasticizer can be used.
  • polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
  • the amount of the plasticizer used is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, and particularly preferably 20 to 120 parts by weight, relative to 100 parts by weight of the polymer (A) having a reactive silicon group. . If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product will be insufficient.
  • a plasticizer may be used individually and may use 2 or more types together.
  • Solvents or diluents may be added to the curable compositions of the present disclosure.
  • Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
  • 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 above solvents or diluents may be used alone or in combination of two or more.
  • An anti-sagging agent may be added to the curable composition according to the present disclosure as necessary to prevent sagging and improve workability.
  • the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
  • the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer (A) having a reactive silicon group.
  • An antioxidant can be used in the curable composition according to the present disclosure.
  • the use of an antioxidant can enhance the weather resistance of the cured product.
  • antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols.
  • Examples include BHT, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520, and SONGNOX 1076.
  • Tinuvin 622LD, Tinuvin 144, Tinuvin 292; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by BASF); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of these are manufactured by Sankyo Lifetech Co., Ltd.); Hindered amines shown in Nocrack CD (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) System light stabilizers can also be used.
  • antioxidants such as SONGNOX4120, NOUGARD 445, and OKABEST CLX050 can also be used.
  • antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • a light stabilizer can be used in the curable compositions according to the present disclosure.
  • the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
  • Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
  • Hindered amine light stabilizers include Tinuvin 123, Tinuvin 144, Tinuvin 249, Tinuvin 292, Tinuvin 312, Tinuvin 622LD, Tinuvin 765, Tinuvin 770, Tinuvin 880, Tinuvin 5866, Tinuvin B97; ADEKA STAB LA-57, LA-62, LA-63, LA-67, LA-68 (both of which are manufactured by ADEKA Co., Ltd.); Sanol LS-292, LS-2626, LS-765, LS-744, LS- 1114 (both of which are manufactured by Sankyo Lifetech Co., Ltd.); lights such as SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB CS622, SONGSORB CS944 (both of which are manufactured by SONGWON), and Nocrac CD (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) Stabilizers can be exe
  • the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • a UV absorber can be used in the curable composition according to the present disclosure.
  • the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
  • Benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based and metal chelate-based compounds can be exemplified as UV absorbers, and benzotriazole-based compounds are particularly preferred.
  • triazine-based compounds include Tinuvin 400, Tinuvin 405, Tinuvin 477, Tinuvin 1577ED (all of which are manufactured by BASF); SONGSORB CS400 and SONGSORB1577 (manufactured by SONGWON).
  • benzophenone compounds include SONGSORB8100 (manufactured by SONGWON).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • Addworks IBC760 (manufactured by Clariant) can also be used as a product in which antioxidants, light stabilizers, and ultraviolet absorbers are mixed.
  • the curable composition according to the present disclosure may optionally contain a physical property modifier for adjusting the tensile properties of the resulting cured product.
  • a physical property modifier for adjusting the tensile properties of the resulting cured product.
  • the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
  • arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
  • the physical property modifiers may be used alone or in combination of two or more.
  • a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the surface stickiness of the cured product.
  • Compounds that generate trimethylsilanol are particularly preferred.
  • examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups.
  • Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.
  • the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • a tackifying resin can be added for the purpose of enhancing the adhesiveness or adhesion to the substrate, or for other purposes.
  • the tackifying resin there is no particular limitation, and those commonly used can be used.
  • terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
  • petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
  • the amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymer (A) having a reactive silicon group. is more preferred. If the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and if the amount exceeds 100 parts by weight, the viscosity of the composition becomes too high and handling may become difficult.
  • Compounds containing epoxy groups can be used in the curable compositions of the present disclosure.
  • the use of a compound having an epoxy group can enhance the restorability of the cured product.
  • Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
  • epoxidized soybean oil epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate , epoxy butyl stearate and the like.
  • the epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polymer (A) having a reactive silicon group.
  • Photocurable materials can be used in the curable compositions of the present disclosure.
  • a photocurable substance When a photocurable substance is used, a film of the photocurable substance 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.
  • Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
  • the photocurable substance is preferably used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. If it is less than 1 part by weight, there is no effect of improving the weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.
  • Oxygen-curable materials can be used in the curable compositions of the present disclosure.
  • oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
  • Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
  • silicone resins obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, 1,4-polybutadiene, C5-C8 diene polymers, etc.
  • diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, 1,4-polybutadiene, C5-C8 diene polymers, etc.
  • liquid polymers These may be used alone or in combination of two or more.
  • the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. weight part. If the amount used is less than 0.1 part by weight, the improvement in staining resistance will not be sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product will tend to be impaired. As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.
  • Epoxy resin can be used in combination with the curable composition according to the present disclosure.
  • a composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles.
  • epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
  • the ratio of (A)/epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of (A)/epoxy resin exceeds 100/1. and the strength of the cured polymer becomes insufficient.
  • a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present disclosure.
  • the epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.
  • the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • the curable composition according to the present disclosure can also be prepared as a one-component type in which all the ingredients are preformed and sealed and cured by moisture in the air after application, and a curing catalyst and filling are separately used as curing agents. It can also be prepared as a two-component type in which components such as the material, plasticizer, and water are blended and the blending materials and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.
  • the ingredients containing water are preliminarily dehydrated and dried before use, or dehydrated by decompression or the like during blending and kneading. is preferred.
  • n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, ⁇ -glycol Addition of an alkoxysilane compound such as sidoxypropyltrimethoxysilane further improves storage stability.
  • the amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight per 100 parts by weight of the polymer (A) having a reactive silicon group. is 0.5 to 10 parts by weight.
  • the curable composition according to the present disclosure includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, and soundproofing materials. It can be used for materials, foam materials, paints, spray materials, etc.
  • a cured product obtained by curing the curable composition according to the present disclosure is excellent in flexibility and adhesiveness, and therefore, among these, it is more preferably used as a sealant or an adhesive.
  • electrical and electronic component materials such as solar cell back sealing materials, electrical and electronic component materials such as insulating coating materials for electric wires and cables, electrical insulating materials for equipment, acoustic insulating materials, elastic adhesives, binders, contact type Adhesives, spray-type sealing materials, crack repair materials, tiling adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical equipment Sealing materials, dental impression materials, food packaging materials, joint sealing materials for 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 , electric and electronic potting agents, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, rust-proof and waterproof sealing materials for wire glass and laminated glass edges (cut parts), automobile parts , trucks, buses and other large vehicle parts, train vehicle parts, aircraft parts, ship parts, electrical parts, various machine parts,
  • the curable compositions of the present disclosure are also used in interior panel adhesives, exterior panel adhesives, tiling adhesives, masonry adhesives, ceiling finish adhesives, floor finish adhesives, wall finish adhesives, adhesives for automobiles, adhesives for vehicle panels, adhesives for assembling electrical, electronic and precision equipment, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure-sensitive adhesives, It can also be used as a sealing material for direct glazing, a sealing material for double glazing, a sealing material for SSG construction method, a sealing material for working joints of buildings, a material for civil engineering, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.
  • [Item 1] having a reactive silicon group of general formula (1), a terminal structure having the reactive silicon group and a terminal olefin group and/or an internal olefin group, the reactive silicon group in the terminal structure; containing a reactive silicon group-containing polyoxyalkylene polymer (A) in which the total number of the terminal olefin groups and the internal olefin groups is more than 1.0 on average per terminal structure; —Si(R 1 ) 3-a X a (1) (R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group.
  • Each X is independently a hydroxyl group or a hydrolyzable group.
  • a is 1, 2, or 3.
  • R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; A is a ⁇ -diketone group.
  • the number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
  • Liquid delivery system Tosoh HLC-8220GPC Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C
  • Average number of reactive silicon groups per terminal structure of the polymer shown in Examples average number of reactive silicon groups per molecule, reactive silicon group per terminal structure, terminal olefin The average total number of groups and internal olefinic groups was calculated from the structure of the polymer and the results of NMR measurements.
  • the unpurified polyoxypropylene thus obtained was mixed with n-hexane and water, and then the water was removed by centrifugation. Removed. As a result, polyoxypropylene (Q-1) having a plurality of carbon-carbon unsaturated bonds at the ends was obtained.
  • Polymer (A-1) has an average total number of reactive silicon groups, terminal olefin groups and internal olefin groups per terminal structure of 2.0 per terminal structure, and 1 trimethoxysilyl group. It was found that each terminal structure has an average of 1.7 and one molecule has an average of 3.4.
  • polystyrene resin To 500 g of this polymer (Q-2) was added 50 ⁇ l of a platinum divinyldisiloxane complex solution (isopropanol solution of 3% by weight in terms of platinum), and 7.5 g of trimethoxysilane was slowly added dropwise while stirring. After the mixed solution was reacted at 90° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to give a polyoxypropylene (A′-1 ).
  • the polymer (A'-1) has an average total number of reactive silicon groups, terminal olefin groups and internal olefin groups per terminal structure of 1.0 per terminal structure, and has a trimethoxysilyl group. It was found that one terminal structure has an average of 0.8 and one molecule has an average of 1.6.
  • Example 1 For 100 parts by weight of the polymer (A-1) obtained in Synthesis Example 1, 100 parts by weight of DINP (manufactured by J-Plus Co., Ltd., diinonyl phthalate), Imerseal 36S (manufactured by Imerys: ground calcium carbonate ) 100 parts by weight, Hakuenka CCR S10 (manufactured by Shiraishi Calcium Co., Ltd.: colloidal calcium carbonate) 200 parts by weight, Tinuvin 326 (manufactured by BASF: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl- 6-tert-butylphenol) 1 part by weight, Tinuvin 770 (manufactured by BASF: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate) 1 part by weight, Irganox 245 (manufactured by BASF: hindered phenolic antioxidant agent) was mixed and uniformly dispersed.
  • DINP manufactured by J
  • Dynasylan VTMO manufactured by EVONIK: vinyltrimethoxysilane
  • Dynasylan AMMO manufactured by EVONIK: 3-aminopropyltrimethoxysilane
  • the catalyst (B-1) obtained in Synthesis Example 3 3.5 parts by weight was added and uniformly mixed and defoamed using a rotation/revolution mixer.
  • the 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 prepare a sheet-like cured product having a thickness of about 3 mm.
  • the sheet-shaped cured product was punched into a No.
  • Example 2 Evaluation was carried out in the same manner as in Example 1, except that 4.5 parts by weight of catalyst (B-1) was added. Table 1 shows the results.
  • Example 2 Evaluation was carried out in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymer (A'-1) and 4.5 parts by weight of the catalyst (B-1) was added. Table 1 shows the results.
  • Example 3 Evaluation was carried out in the same manner as in Example 1 except that the catalyst (B-1) was changed to 0.3 parts by weight of TIB KAT 223 (dioctyltin dicetylacetonate manufactured by TIB Chemical). Table 1 shows the results.
  • Example 4 Evaluation was carried out in the same manner as in Example 1 except that the polymer (A-1) was changed to the polymer (A'-1) and the catalyst (B-1) was changed to 0.3 parts by weight of TIB KAT 223. . Table 1 shows the results.
  • Examples 1 and 2 containing a reactive silicon group-containing polyoxyalkylene polymer (A) and a reaction product of a titanium compound (B) and ammonium hydroxide (C) are comparative examples that do not contain either Compared to 1 to 4, the breaking strength and breaking elongation in the dumbbell tensile test are improved.

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Abstract

L'invention concerne une composition durcissable contenant : un polymère de polyoxyalkylène contenant un groupe silicium réactif (A) ayant un groupe silicium réactif, une structure terminale comprenant le groupe silicium réactif et un groupe oléfine terminal et/ou un groupe oléfine interne, et le nombre total du groupe silicium réactif, du groupe oléfine terminal et du groupe oléfinique interne dans la structure terminale étant supérieur à 1,0, en moyenne, par structure terminale unique ; et un composé de titane (B) et de l'hydroxyde d'ammonium (C), ou un produit de réaction résultant d'une réaction entre le composé de titane (B) et l'hydroxyde d'ammonium (C).
PCT/JP2022/036817 2021-10-01 2022-09-30 Composition durcissable WO2023054701A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391529A (zh) * 2011-07-14 2012-03-28 杭州师范大学 一种封装用硅树脂型有机无机杂化材料制备方法
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
CN103694888A (zh) * 2013-12-17 2014-04-02 中昊北方涂料工业研究设计院有限公司 一种含硅透明耐磨涂料及其制备方法
WO2015080067A1 (fr) * 2013-11-29 2015-06-04 株式会社カネカ Composition durcissable
WO2016002907A1 (fr) * 2014-07-02 2016-01-07 株式会社カネカ Composition durcissable et objet durci obtenu à partir de celle-ci
CN108329473A (zh) * 2017-01-20 2018-07-27 中国科学院化学研究所 一种含有高苯基聚硅氧烷的组合物和包括该组合物的封装材料或光学薄膜
WO2021106942A1 (fr) * 2019-11-29 2021-06-03 日東化成株式会社 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, composition durcissable à l'humidité, et procédé de production d'un produit durci
WO2021106943A1 (fr) * 2019-11-29 2021-06-03 日東化成株式会社 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, procédé de production dudit catalyseur de durcissement, composition durcissable à l'humidité, et procédé de production d'article durci

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391529A (zh) * 2011-07-14 2012-03-28 杭州师范大学 一种封装用硅树脂型有机无机杂化材料制备方法
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
WO2015080067A1 (fr) * 2013-11-29 2015-06-04 株式会社カネカ Composition durcissable
CN103694888A (zh) * 2013-12-17 2014-04-02 中昊北方涂料工业研究设计院有限公司 一种含硅透明耐磨涂料及其制备方法
WO2016002907A1 (fr) * 2014-07-02 2016-01-07 株式会社カネカ Composition durcissable et objet durci obtenu à partir de celle-ci
CN108329473A (zh) * 2017-01-20 2018-07-27 中国科学院化学研究所 一种含有高苯基聚硅氧烷的组合物和包括该组合物的封装材料或光学薄膜
WO2021106942A1 (fr) * 2019-11-29 2021-06-03 日東化成株式会社 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, composition durcissable à l'humidité, et procédé de production d'un produit durci
WO2021106943A1 (fr) * 2019-11-29 2021-06-03 日東化成株式会社 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, procédé de production dudit catalyseur de durcissement, composition durcissable à l'humidité, et procédé de production d'article durci

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