Classifications

• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

• the present invention relates to a curable composition and its cured product.
• Sealing materials are known as building materials that can be suitably used for exterior wall joints, repairing cracks, joints in reinforced concrete structures, around sashes, etc.
• Patent Document 1 discloses polyalkylene oxide containing a dimethoxymethylsilyl group and having a main chain skeleton made of polypropylene oxide, polypropylene glycol, colloidal calcium carbonate, ground calcium carbonate, a dehydrating agent, and a hinder.
• a curable composition comprising a dophenolic antioxidant is disclosed.
• Patent Document 2 discloses an oxyalkylene polymer having a crosslinkable silicon group, an alkoxysilane compound that reacts with water to produce an amine compound having an alkoxysilyl group, a tetravalent tin compound, and a (meth)acrylic compound. Buildings having walled structures using one-component sealants containing acid ester polymer plasticizers are disclosed.
• one aspect of the present invention is to provide a curable composition having excellent physical properties such as low modulus, high strength, and high elongation when cured even when a high amount of filler such as calcium carbonate is blended. With the goal.
• the present inventors have studied to solve the above problems, and as a result, by blending a predetermined weight part of a polyoxyalkylene polymer having a specific reactive silicon group, a specific polypropylene glycol, and a dehydrating agent, The inventors have found new knowledge that low modulus, high strength, and high elongation can be achieved even when a high amount of filler such as calcium carbonate is blended, and have completed the present invention.
• one aspect of the present invention comprises (A) 100 parts by weight of a polyoxyalkylene polymer having a reactive silicon group, (B) 120 to 300 parts by weight of polypropylene glycol having a molecular weight of 2000 or more, and (C) colloidal carbonic acid. 40 to 250 parts by weight of calcium, (D) 80 to 300 parts by weight of ground calcium carbonate, and (E) 4 parts by weight or more of a dehydrating agent, wherein the polymer (A) is contained in one molecule.
• a curable composition ( Hereinafter, it is called "this curable composition”.).
• a curable composition having excellent physical properties such as low modulus, high strength, and high elongation when cured even when a high amount of filler such as calcium carbonate is blended. can be done.
• the present inventors have made intensive studies and found that a polyoxyalkylene polymer having a specific reactive silicon group, a specific polypropylene glycol, and a dehydrating agent are added to a predetermined
• the present inventors have found new knowledge that by blending parts by weight, low modulus, high strength, and high elongation can be achieved even when a high amount of filler such as calcium carbonate is blended.
• At least two types of polyoxyalkylene polymers having specific reactive silicon groups (a linear polymer with a high content of reactive silicon groups (highly silylated polymer) and
• a linear polymer with a low silylation content (low silylation polymer)
• the modulus tends to be high when only a high silylation polymer is used, but the linear high silyl content Modulus can be improved without sacrificing strength and elongation by blending low silylation polymers with linear low silylation polymers.
• desired physical properties can be achieved while a high amount of filler such as calcium carbonate is blended into the curable composition, so cost reduction can be achieved, which is extremely advantageous in the field of sealants and the like. .
• the present curable composition is a polyoxyalkylene polymer (A1) having a specific structure (that is, a linear structure containing an average of 1.6 or more reactive silicon groups in one molecule) (hereinafter simply referred to as Sometimes referred to as “polyoxyalkylene polymer (A1)” or “polymer (A1)”) and a specific structure (i.e., containing less than 1.6 reactive silicon groups on average per molecule
• a polyoxyalkylene polymer (A2) hereinafter simply referred to as “polyoxyalkylene polymer (A2)” or “polymer (A2)” having a linear structure) and include.
• the curable composition contains the polyoxyalkylene-based polymer (A1) and the polyoxyalkylene-based polymer (A2), so that when the curable composition is cured, a low modulus , high strength and high elongation.
• a polyoxyalkylene polymer (A1) having a linear structure containing an average of 1.6 or more reactive silicon groups per molecule and an average of 1.6 reactive silicon groups per molecule.
• A a polyoxyalkylene-based polymer having a reactive silicon group, which contains a polyoxyalkylene-based polymer (A2) having a linear structure containing less than 6, "polyoxyalkylene-based polymer (A )” and “Polymer (A)”.
• the polyoxyalkylene polymer (A1) has a straight chain structure containing an average of 1.6 or more reactive silicon groups per molecule.
• the polyoxyalkylene-based polymer (A1) has at least one reactive silicon group in the molecular chain, a silanol condensation reaction occurs to crosslink it, turn it into a polymer state, and cure it.
• the number of reactive silicon groups contained in the polyoxyalkylene polymer (A1) must be at least 1 from the viewpoint of condensation reaction with a silanol condensation catalyst. Alternatively, it is preferable that reactive silicon groups are present at both ends of the branched molecular chain.
• the reactive silicon group contained in the polyoxyalkylene polymer (A1) has a hydroxy group or hydrolyzable group bonded to the silicon atom, and forms a siloxane bond through a reaction accelerated by a silanol condensation catalyst. It is a group that can be crosslinked by means of
• the polyoxyalkylene polymer (A1) has a reactive silicon group represented by general formula (1).
• —Si(R) 3-a (X) a (1)
• each R is independently a hydrocarbon group having 1 to 20 carbon atoms, or —OSi(R′) 3 (R′ is each independently a hydrocarbon group having 1 to 20 carbon atoms.
• the hydrocarbon group as R may be substituted and may have a hetero-containing group.
• X is each independently a hydroxyl group or a hydro is a degradable group.
• a is an integer of 1 to 3.
• the number of carbon atoms in the hydrocarbon group of R is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.
• R include, for example, methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group, preferably methyl group, ethyl group and chloromethyl group. , a methoxymethyl group, more preferably a methyl group or a methoxymethyl group. According to the said structure, it has the advantage that it is easy to balance storage stability and reactivity.
• 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 such as a methoxy group and an ethoxy group is more preferred, and a methoxy group and an ethoxy group are particularly preferred, since they are moderately hydrolyzable and easy to handle.
• Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (A1) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and dimethoxymethyl silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N ,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto.
• methyldimethoxysilyl trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- Diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with high rigidity can be obtained. A trimethoxysilyl group is more preferred.
• the polyoxyalkylene polymer (A1) may have an average of more than one reactive silicon group at one terminal site.
• "having an average of more than one reactive silicon group at one terminal site” means that the polyoxyalkylene polymer (A1) has the following general formula (2) It shows that one terminal portion contains a polyoxyalkylene having two or more reactive silicon groups. That is, the polyoxyalkylene polymer (A1) may contain only a polyoxyalkylene having two or more reactive silicon groups at one terminal site, or two or more at one terminal site. and polyoxyalkylenes having one reactive silicon group at one terminal site.
• the plurality of terminal sites possessed by one molecule of polyoxyalkylene may include both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group.
• the polyoxyalkylene polymer (A1) as a whole has an average of more than one reactive silicon group at one terminal site, but a poly having a terminal site without a reactive silicon group It may contain oxyalkylene.
• the terminal portion of the polyoxyalkylene polymer (A1) has the general formula (2):
• R 1 and R 3 are each independently a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen , nitrogen, each of R 2 and R 4 is independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10, R 5 is a substituted or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and c is an integer of 1 to 3.).
• R 1 and R 3 may be a divalent organic group having 1 to 6 carbon atoms, may contain an oxygen atom, or may be a hydrocarbon group.
• the number of carbon atoms in the hydrocarbon group is preferably 1-4, more preferably 1-3, even more preferably 1-2.
• Specific examples of R 1 include CH 2 OCH 2 , CH 2 O and CH 2 , preferably CH 2 OCH 2 .
• Specific examples of R 3 include CH 2 and CH 2 CH 2 , preferably CH 2 .
• the number of carbon atoms in the hydrocarbon groups of R 2 and R 4 is preferably 1-5, more preferably 1-3, even more preferably 1-2.
• Specific examples of R 2 and R 4 include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom and a methyl group, more preferably a hydrogen atom.
• the terminal moiety represented by the general formula (2) is CH 2 OCH 2 for R 1 , CH 2 for R 3 , and hydrogen atoms for R 2 and R 4 .
• n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
• n is not limited to one value, and may be a mixture of multiple values.
• the number of reactive silicon groups possessed by the polyoxyalkylene polymer (A1) is preferably more than 1.0 on average at one terminal site, more preferably 1.1 or more. , is more preferably 1.5 or more, and even more preferably 2.0 or more. Also, the number is preferably 5 or less, more preferably 3 or less.
• the number of terminal sites having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A1) is preferably 0.5 or more on average, and 1.0 It is more preferably 1 or more, still more preferably 1.1 or more, and even more preferably 1.5 or more. Also, the number is preferably 4 or less, more preferably 3 or less.
• the polyoxyalkylene polymer (A1) may have reactive silicon groups in addition to the terminal sites, but having only the terminal sites provides a rubber-like cured product with high elongation and low elastic modulus. It is preferable because it becomes easy to be
• the average number of reactive silicon groups in one molecule of the polyoxyalkylene polymer (A1) is 1.6 or more, preferably 1.8 or more, and 2.0 or more. is more preferable, and 2.5 or more is even more preferable.
• the number of reactive silicon groups is 1.6 or more on average, the effect of increasing the strength of the curable composition is exhibited.
• the upper limit is not particularly limited, it is, for example, 5.0 or less on average, preferably 4.5 or less. When the upper limit is 5.0 or less, the effect of providing a flexible elastic body is exhibited.
• the main chain skeleton of the polyoxyalkylene polymer (A1) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, Examples include polyoxypropylene-polyoxybutylene copolymers. Among them, polyoxypropylene is preferred.
• the number average molecular weight of the polyoxyalkylene polymer (A1) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene equivalent molecular weight in GPC. If the number average molecular weight is less than 3,000, the amount of reactive silicon groups to be introduced increases, which may be disadvantageous in terms of production costs. There is
• the organic polymer precursor before introduction of the reactive silicon group was subjected to the hydroxyl value measurement method of JIS K 1557 and the iodine value of JIS K 0070.
• the terminal group concentration was measured by titration analysis based on the principle of the measurement method, and indicate the terminal group equivalent molecular weight obtained by considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used).
• the terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A1) is obtained by preparing a calibration curve of the number-average molecular weight obtained by general GPC measurement of the organic polymer precursor and the terminal-group-equivalent molecular weight, and calculating the polyoxyalkylene-based It is also possible to convert the number average molecular weight obtained by GPC of the polymer (A1) into a terminal group equivalent molecular weight.
• the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A1) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, and even more preferably 1.5 or less. , 1.4 or less is particularly preferred, and 1.2 or less is most preferred.
• the molecular weight distribution of the polyoxyalkylene polymer (A1) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the main chain structure of the polyoxyalkylene polymer (A1) is a linear structure.
• the viscosity of the polyoxyalkylene polymer (A1) is not particularly limited, but is preferably 1 Pa s to 5 Pa s, more preferably 1.5 Pa s to 4 Pa s, and further 2 Pa s to 3 Pa s. preferable.
• the viscosity of the polyoxyalkylene-based polymer (A1) is 1 Pa ⁇ s to 5 Pa ⁇ s, there is an advantage that the strength increases when the curable composition is cured.
• Introduction of a reactive silicon group to the main chain of the polyoxyalkylene polymer (A1) may be performed by a known method. For example, the following methods are mentioned.
• Method I An organic polymer having a functional group such as a hydroxy group is reacted with a compound having an active group that exhibits reactivity with the functional group and an unsaturated group to obtain an organic polymer having an unsaturated group. Then, the resulting organic polymer having unsaturated groups is reacted with a hydrosilane compound having reactive silicon groups by hydrosilylation.
• Examples of compounds having a reactive active group and an unsaturated group that can be used in Method I include unsaturated group-containing epoxy compounds such as allyl glycidyl ether, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, Examples thereof include compounds having a carbon-carbon double bond such as methallyl bromide, vinyl iodide, allyl iodide and methallyl iodide.
• Examples of compounds having a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- 2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-p
• Halogenated hydrocarbon compounds having a carbon-carbon triple bond as well as compounds such as vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Hydrocarbon compounds with unsaturated bonds other than halogenated hydrocarbons with carbon-carbon triple bonds may also be used.
• hydrosilane compounds that can be used in method I include halogenated silanes, alkoxysilanes, acyloxysilanes, ketoximate silanes, and the like. Hydrosilane compounds are not limited to these.
• halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.
• alkoxysilanes include trimethoxysilane, triethoxysilane, triisopropoxysilane, dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, (methoxymethyl)dimethoxysilane, phenyldimethoxysilane, 1-[ 2-(Trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane and the like.
• acyloxysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.
• ketoximate silanes include bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane.
• halogenated silanes and alkoxysilanes are particularly preferred.
• Alkoxysilanes are most preferred because they are mildly hydrolyzable and easy to handle.
• alkoxysilanes it is easy to obtain, it is easy to obtain a resin composition for foams with excellent curability and storage stability, and it is possible to produce foams with excellent tensile strength using the resin composition for foams.
• Dimethoxymethylsilane is preferred because it is easy to use.
• Trimethoxysilane and triethoxysilane are also preferable from the viewpoint of easily obtaining a resin composition for foam having excellent curability.
• Method II A compound having a mercapto group and a reactive silicon group is subjected to a radical addition reaction in the presence of a radical initiator and/or a radical generating source to obtain an organic polymer having an unsaturated group in the same manner as in Method I.
• Compounds having a mercapto group and a reactive silicon group that can be used in Method II include, for example, 3-mercapto-n-propyltrimethoxysilane, 3-mercapto-n-propylmethyldimethoxysilane, 3-mercapto-n-propyl triethoxysilane, 3-mercapto-n-propylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane and the like.
• Compounds having mercapto groups and reactive silicon groups are not limited to these.
• Method III A method of reacting an organic polymer having functional groups such as hydroxy, epoxy, and isocyanate groups in the molecule with a compound having a functional group reactive to these functional groups and a reactive silicon group. .
• the method of reacting an organic polymer having a hydroxy group with a compound having an isocyanate group and a reactive silicon group, which can be employed in Method III, is not particularly limited. and the like.
• Compounds having isocyanate groups and reactive silicon groups that can be used in Method III include, for example, 3-isocyanato-n-propyltrimethoxysilane, 3-isocyanato-n-propylmethyldimethoxysilane, 3-isocyanato-n- Propyltriethoxysilane, 3-isocyanato-n-propylmethyldiethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane and the like.
• Compounds having isocyanate groups and reactive silicon groups are not limited to these.
• Silane compounds such as trimethoxysilane, in which three hydrolyzable groups are bonded to one silicon atom, may undergo a disproportionation reaction. As the disproportionation reaction progresses, unstable compounds such as dimethoxysilane are produced, which can be difficult to handle. However, such a disproportionation reaction does not proceed with 3-mercapto-n-propyltrimethoxysilane and 3-isocyanato-n-propyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups are bonded to one silicon atom, such as a trimethoxysilyl group, is used as the silicon-containing group, method II or method III is preferably used.
• the disproportionation reaction does not proceed with the silane compound represented by the following formula (2a).
• X is the same as in formula (1a).
• 2m+2 R 2a are independently the same as R 1a in Formula (1a).
• R 3a represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• m represents an integer of 0 or more and 19 or less.
• R 2a are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms. A hydrocarbon group having 1 or more and 4 or less atoms is more preferable.
• R 3a is preferably a divalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 8 carbon atoms, and a divalent hydrocarbon group having 2 carbon atoms. groups are more preferred.
• m is most preferably 1.
• Silane compounds represented by formula (2a) include, for example, 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl) propyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl)hexyl]-1,1,3,3-tetramethyldisiloxane and the like.
• Method I or Method III the method of reacting an organic polymer having a terminal hydroxy group with a compound having an isocyanate group and a reactive silicon group provides a high conversion rate in a relatively short reaction time.
• the organic polymer having a reactive silicon group obtained by Method I has a lower viscosity than the organic polymer having a reactive silicon group obtained by Method III, and the resin composition for foams has good workability. is obtained, and the organic polymer having a reactive silicon group obtained by Method II has a strong odor due to mercaptosilane. Therefore, Method I is particularly preferred.
• a synthetic method for introducing an average of more than 1.0 reactive silicon groups to one terminal site of a polyoxyalkylene polymer will be described below.
• the polyoxyalkylene polymer (A1) having an average of more than 1.0 reactive silicon groups at one terminal site has two at one terminal of the hydroxyl group-terminated polymer obtained by polymerization. After introducing the above carbon-carbon unsaturated bonds, it is preferable to react with a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bonds.
• the polyoxyalkylene polymer (A1) is preferably produced by polymerizing an epoxy compound with an initiator having a hydroxyl group using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex.
• hydroxyl-containing initiators include hydroxyl groups such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, and polypropylene monoalkyl ether. Examples include those having one or more.
• epoxy compounds include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.
• alkali metal salt used in the present invention sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferred, and sodium methoxide and potassium methoxide are more preferred.
• Sodium methoxide is particularly preferred because of its availability.
• the temperature at which the alkali metal salt is allowed to act is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°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.
• epoxy compound having a carbon-carbon unsaturated bond used in the present invention, especially general formula (3):
• R 1 and R 2 in the formula are the same as the substituents described above.
• allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.
• the 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 molar ratio of the hydroxyl group-terminated polymer to the hydroxyl group is preferably 0.2 or more, more preferably 0.5 or more. Also, it is preferably 5.0 or less, more preferably 2.0 or less.
• the reaction temperature for the ring-opening addition reaction of an epoxy compound having a carbon-carbon unsaturated bond with a polymer containing a hydroxyl group is preferably 60° C. or higher and 150° C. or lower. It is more preferably 110° C. or higher and 140° C. or lower.
• halogenated hydrocarbon compounds having a carbon-carbon unsaturated bond examples include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, and allyl iodide. , methallyl iodide, etc., and it is more preferable to use allyl chloride and methallyl chloride from the viewpoint of ease of handling.
• the amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the molar ratio to the hydroxyl group of the hydroxyl-terminated polymer is preferably 0.7 or more, and 1.0 or more. more preferred. Moreover, 5.0 or less is preferable and 2.0 or less is more preferable.
• 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, more preferably 110°C or higher and 140°C or lower.
• the reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.
• the polyoxyalkylene polymer (A2) has a linear structure containing less than 1.6 reactive silicon groups on average per molecule.
• the average number of reactive silicon groups in one molecule of the polyoxyalkylene polymer (A2) is less than 1.6, preferably 1.5 or less, and 1.4 or less. is more preferable. When the average number of reactive silicon groups is less than 1.6, an effect of high elongation is obtained.
• the lower limit is not particularly limited, it is, for example, 0.5 or more on average, preferably 0.6 or more. When the lower limit is 0.6 or more, the tackiness is good.
• the viscosity of the polyoxyalkylene polymer (A2) is not particularly limited, but is preferably 6.0 Pa s to 50 Pa s, more preferably 7.0 Pa s to 48 Pa s, and 8.0 Pa s to 45 Pa. • s is more preferred.
• the viscosity of the polyoxyalkylene polymer (A2) is 6.0 Pa ⁇ s to 50 Pa ⁇ s, physical properties such as low modulus and high elongation can be obtained when the curable composition is cured.
• polyoxyalkylene polymer (A2) for example, JP-B-45-36319, JP-B-46-12154, JP-A-50-156599, JP-A-54-6096, JP-A-55-13767, JP-A-55-13468, JP-A-57-164123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. Polymers and the like proposed in publications such as No. 4960844 can be mentioned.
• the weight ratio of the polyoxyalkylene polymer (A1) and the polyoxyalkylene polymer (A2) is preferably 95:5 to 30:70, more preferably 90:10 to 40:60. and more preferably 80:20 to 50:50.
• the weight ratio of the polyoxyalkylene polymer (A1) to the polyoxyalkylene polymer (A2) is 95:5 to 30:70, the strength and elongation are well balanced.
• the curable composition contains polypropylene glycol with a molecular weight of 2000 or greater.
• polypropylene glycol intends a thermoplastic resin that is a polymerized polymer of propylene.
• the molecular weight of polypropylene glycol is 2,000 or more, preferably 2,500 or more, and more preferably 3,000 or more. When the molecular weight of the polypropylene glycol is 2000 or more, the effect of low contamination is exhibited.
• the upper limit of the molecular weight of the polypropylene glycol is not particularly limited, it is, for example, 15,000 or less, preferably 10,000 or less. When the upper limit of the molecular weight of the polypropylene glycol is 15000 or less, the effect of low viscosity is exhibited.
• polypropylene glycol with a molecular weight of 2000 or more can be used.
• examples of commercially available polypropylene glycol having a molecular weight of 2000 or more include Sannix PP-3000 (manufactured by Sanyo Chemical Industries) and Actcol P-3030 (manufactured by Mitsui Chemicals).
• Polypropylene glycol having a molecular weight of 2000 or more may be used alone or in combination of two or more.
• the blending amount of polypropylene glycol is 120 to 300 parts by weight, preferably 125 to 280 parts by weight, more preferably 130 to 260 parts by weight, with respect to 100 parts by weight of the total polyoxyalkylene polymer (A).
• the blending amount of polypropylene glycol is 120 to 300 parts by weight, there is an advantage in terms of flexibility.
• the curable composition comprises colloidal calcium carbonate. Cost reduction can be achieved by including colloidal calcium carbonate in the present curable composition. In addition, since the present curable composition contains colloidal calcium carbonate, it is possible to reduce slip and slump that occur when used for vertical joints under high temperature conditions.
• the colloidal calcium carbonate is not particularly limited, but examples include mechanically pulverized and processed limestone. Only one type of colloidal calcium carbonate may be used, or two or more types may be used in combination.
• the specific surface area of colloidal calcium carbonate is preferably 1 to 100 m 2 /g, more preferably 10 to 50 m 2 /g.
• the specific surface area of the colloidal calcium carbonate (C) is determined by a powder specific surface area measuring device.
• the average particle size of colloidal calcium carbonate is preferably 0.01-0.5 ⁇ m, more preferably 0.02-0.1 ⁇ m.
• the average particle size of colloidal calcium carbonate is calculated from the specific surface area. The strength of the cured product tends to increase as the average particle size decreases.
• the colloidal calcium carbonate may be surface-treated or untreated.
• surface treatment agents used for surface treatment of colloidal calcium carbonate include organic substances, various surfactants (fatty acids, fatty acid soaps, fatty acid esters, etc.), and various coupling agents (silane coupling agents, titanate coupling agents, etc.). etc.
• the colloidal calcium carbonate is preferably treated with a surface treatment agent in an amount of 0.1 to 20% by weight, based on the weight of the colloidal calcium carbonate, and is treated with a surface treatment agent in an amount of 0.2 to 10% by weight. is more preferable.
• the amount of the surface treatment agent used is 0.1% by weight or more, the effect of improving workability and adhesiveness is good.
• the amount of the surface treatment agent used is 20% by weight or less, the storage stability of the curable composition is good.
• the amount of colloidal calcium carbonate compounded is 40 to 250 parts by weight, preferably 50 to 240 parts by weight, more preferably 60 to 230 parts by weight, with respect to 100 parts by weight of the total amount of the polyoxyalkylene polymer (A). .
• the content of colloidal calcium carbonate is 40 to 250 parts by weight, it has the advantages of high strength and high elongation.
• the curable composition comprises ground calcium carbonate. Cost reduction can be achieved by including heavy calcium carbonate in the present curable composition.
• the heavy calcium carbonate is not particularly limited, but examples include those obtained by mechanically pulverizing and processing limestone, shells, chalk, marble, and the like. Only one type of ground calcium carbonate may be used, or two or more types may be used in combination.
• the specific surface area of heavy calcium carbonate is preferably 1.0 to 3.5 m 2 /g, more preferably 1.2 to 3.0 m 2 /g.
• the specific surface area of heavy calcium carbonate is determined by a powder specific surface area measuring device.
• the average particle size of heavy calcium carbonate is preferably 0.8-5.0 ⁇ m, more preferably 1.0-3.0 ⁇ m.
• the average particle size of heavy calcium carbonate is calculated from the specific surface area. The strength of the cured product tends to increase as the average particle size decreases.
• the ground calcium carbonate may be surface-treated or untreated.
• surface treatment agents used for surface treatment of heavy calcium carbonate include organic substances, various surfactants (fatty acids, fatty acid soaps, fatty acid esters, etc.), various coupling agents (silane coupling agents, titanate coupling agents, etc.). ) and the like.
• the ground calcium carbonate is preferably treated with a surface treatment agent in an amount of 0.1 to 20% by weight, based on the weight of the ground calcium carbonate, and is treated with a surface treatment agent in an amount of 1 to 5% by weight. is more preferable.
• the amount of the surface treatment agent used is 0.1% by weight or more, the effect of improving workability and adhesiveness is good.
• the amount of the surface treatment agent used is 20% by weight or less, the storage stability of the curable composition is good.
• the blending amount of heavy calcium carbonate is 80 to 300 parts by weight, preferably 85 to 290 parts by weight, more preferably 90 to 280 parts by weight, with respect to 100 parts by weight of the total polyoxyalkylene polymer (A). preferable.
• the blending amount of heavy calcium carbonate is 80 to 300 parts by weight, it has the advantage of low viscosity.
• the total amount of colloidal calcium carbonate and ground calcium carbonate is 250 parts by weight or more and 260 parts by weight with respect to 100 parts by weight of the total amount of the polyoxyalkylene polymer (A). Above is preferable, and 270 parts by weight or more is more preferable.
• a total amount of colloidal calcium carbonate and ground calcium carbonate of 250 parts by weight has the advantage of low cost.
• the upper limit of the total amount of colloidal calcium carbonate and ground calcium carbonate is not particularly limited, it is, for example, 700 parts by weight or less, preferably 500 parts by weight or less. Slip resistance is excellent when the total amount of colloidal calcium carbonate and ground calcium carbonate is 700 parts by weight or less.
• the curable composition contains a dehydrating agent. Storage stability can be improved by including a dehydrating agent in the present curable composition.
• dehydrating agents include alkoxysilane compounds, synthetic zeolite, activated alumina, silica gel, quicklime, and magnesium oxide.
• alkoxysilane compounds can be suitably used.
• alkoxysilane compounds include n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, ⁇ -glycerol. and sidoxypropyltrimethoxysilane.
• vinyltrimethoxysilane has a high dehydration effect and can be preferably used. Only one type of dehydrating agent may be used, or two or more types may be used in combination.
• a commercially available dehydrating agent may be used, or a synthetic one may be used.
• Examples of commercially available dehydrating agents include vinylsilane A-171 manufactured by Momentive, VTMO manufactured by EVONIK, and KBM-1003 manufactured by Shin-Etsu Silicone.
• the amount of the dehydrating agent is 4 parts by weight or more, preferably 4.2 parts by weight or more, more preferably 4.4 parts by weight or more, with respect to 100 parts by weight of the total amount of the polyoxyalkylene polymer (A). .
• the amount of the dehydrating agent is 4 parts by weight or more, there is an advantage of stable storage.
• the upper limit of the amount of the dehydrating agent is not particularly limited, it is, for example, 10 parts by weight or less, preferably 7 parts by weight or less.
• the amount of the dehydrating agent to be blended is 10 parts by weight or less, a curing speed suitable for the sealant can be achieved.
• the curable composition preferably contains an antioxidant having four hindered phenol structures in one molecule.
• Weather resistance and moisture resistance can be improved by including an antioxidant in the present curable composition. As a result, it can be suitably used in tropical regions such as Southeast Asia, for example.
• the antioxidant has a hindered phenol structure that is a single hindered phenol structure. is preferably
• antioxidants include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di-or tri-) ( ⁇ -methylbenzyl)phenol, 2,2′-methylenebis(4ethyl-6-t-butylphenol), 2,2′-methylenebis(4methyl-6-t-butylphenol), 4,4′-butylidenebis(3- methyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tri Ethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4- hydroxyphenyl
• antioxidants or synthesized antioxidants may be used.
• Commercially available antioxidants include, for example, Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, and Nocrac NS-7.
• Nocrac DAH (all of the above are manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.); 658, ADEKA STAB AO-80, ADEKA STAB AO-15, ADEKA STAB AO-18, ADEKA STAB AO-18, ADEKA STAB 328, ADEKA STAB AO-37 (all manufactured by ADEKA Co., Ltd.); IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Ciba Specialty Chemicals); SumilizerGM, SumilizerGA-80, Sum ilizer GS (all of which are manufactured by Sumitomo Chemical Co., Ltd.).
• the amount of the antioxidant compounded is, for example, 0.2 to 5 parts by weight, preferably 0.4 to 4.5 parts by weight, with respect to 100 parts by weight of the total amount of the polyoxyalkylene polymer (A). 0.6 to 4 parts by weight is more preferred. When the blending amount of the antioxidant is 0.2 to 5 parts by weight, the weather resistance and humidity resistance can be favorably improved.
• the curable composition preferably comprises organic balloons.
• Organic balloons can also be referred to as plastic microballoons. Inclusion of organic balloons in the present curable composition improves thermal insulation.
• organic balloons include, but are not limited to, phenol resin balloons, epoxy resin balloons, urea resin balloons, polyvinylidene chloride resin balloons, polyvinylidene chloride-(meth)acrylic resin balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl Examples include alcohol balloons, styrene-(meth)acrylic resin balloons, polyacrylonitrile balloons, and the like. Only one type of organic balloon may be used, or two or more types may be used in combination. By combining with inorganic balloons such as glass balloons and shirasu balloons, hardness and stringiness can be improved.
• organic balloons or synthesized ones may be used.
• Commercially available organic balloons include, for example, MFL-HD60CA, MFL-81GCA (all manufactured by Matsumoto Yushi), EMC-40 (B) (manufactured by Nippon Philite), and the like.
• the amount of the organic balloon compounded is, for example, 3 to 15 parts by weight, preferably 4 to 12 parts by weight, more preferably 5 to 10 parts by weight, with respect to 100 parts by weight of the total amount of the polyoxyalkylene polymer (A). preferable.
• the amount of the organic balloon is 3 to 15 parts by weight, it has the advantage of improving the heat insulating properties.
• the curable composition may contain other components in addition to the above components (A) to (G).
• Other components are not particularly limited as long as they are commonly added to curable compositions used in the field of sealants and the like.
• Other components include, for example, light stabilizers, adhesion imparting agents, thixotropic agents, pigments, ultraviolet absorbers, curing catalysts, matting agents and the like.
• the blending amount of other components is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately set by those skilled in the art.
• Applications of the present curable composition are not particularly limited, but examples thereof include sealing materials, coating materials, adhesives, paints, waterproofing agents, potting agents and the like. Among others, it is preferably used as a sealant, and more preferably used as a joint structural sealant.
• a cured product (hereinafter referred to as "main cured product") is provided by curing the present curable composition.
• the cured product is formed by curing the curable composition.
• the method of curing the present curable composition is not particularly limited, but for example, a method of curing the present curable composition with moisture in the air, a booster method of forcibly kneading moisture with a static mixer, heating with an oven or heat gun and a method of positively supplying water to the surface by spraying or the like.
• the modulus of the cured product is preferably 0.4 MPa or less, more preferably 0.35 MPa or less, and even more preferably 0.30 MPa or less.
• the lower limit of the modulus of the hardened product is, for example, 0.20 MPa or more, preferably 0.22 MPa or more, and more preferably 0.25 MPa or more.
• the modulus of the main cured product is 0.20 MPa or more, the effect of low contamination is exhibited.
• the modulus of the cured product can be measured by the method described in Examples below.
• the strength of the hardened product is preferably 1.0 MPa or more, more preferably 1.1 MPa or more, and even more preferably 1.3 MPa or more. When the strength of the hardened product is 1.0 MPa or more, the effect of high durability is exhibited.
• the upper limit of the strength of the hardened product is, for example, 3.0 MPa or less, preferably 2.5 MPa or less, and more preferably 2.0 MPa or less. When the strength of the hardened product is 3.0 MPa or less, the effect of preventing the frame from breaking is exhibited.
• the strength of the cured product can be measured by the method described in Examples below.
• the elongation of the cured product is preferably 500% or more, more preferably 600% or more, and even more preferably 700% or more.
• the upper limit of elongation of the cured product is, for example, 1500% or less, preferably 1200% or less, and more preferably 1000% or less.
• the elongation of the main cured product is 1500% or less, the effect of low staining is exhibited.
• the elongation of the cured product can be measured by the method described in Examples below.
• one aspect of the present invention includes the following. ⁇ 1> (A) 100 parts by weight of a polyoxyalkylene polymer having a reactive silicon group, (B) 120 to 300 parts by weight of polypropylene glycol having a molecular weight of 2000 or more; (C) 40 to 250 parts by weight of colloidal calcium carbonate; (D) 80 to 300 parts by weight of ground calcium carbonate, and (E) 4 parts by weight or more of a dehydrating agent,
• the polymer (A) is a linear polyoxyalkylene polymer (A1) containing an average of 1.6 or more reactive silicon groups per molecule; a linear polyoxyalkylene polymer (A2) containing an average of less than 1.6 reactive silicon groups per molecule;
• the curable composition wherein the total amount of the colloidal calcium carbonate (C) and the ground calcium carbonate (D) is 250 parts by weight or more.
• ⁇ 2> The curable composition according to ⁇ 1>, wherein the weight ratio of (A1) and (A2) is 95:5 to 30:70.
• ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, further comprising (F) an antioxidant having four hindered phenol structures in one molecule.
• ⁇ 4> The curable composition according to any one of ⁇ 1> to ⁇ 3>, further comprising (G) an organic balloon.
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer (A1) has a structure represented by the following general formula (2).
• R 1 and R 3 are each independently a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R 1 and R 3 are carbon, oxygen , nitrogen, each of R 2 and R 4 is independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10, R 5 is a substituted or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and c is an integer of 1 to 3; ⁇ 6> The curable composition according to any one of ⁇ 3> to ⁇ 5>, wherein the hindered phenol structure of (F) is a single hindered phenol structure.
• C2 Colloidal calcium carbonate (C2): Made by Shiraishi Calcium, Hakuenka CCR (Heavy calcium carbonate (D)) ⁇ Made by Omya, OMYACARB 1T (Thixotropic agent) ⁇ Arkema amide wax, Crayvallac SL (pigment) ⁇ Titanium oxide manufactured by Ishihara Sangyo, R820 (Organic balloon (G)) ⁇ Organic balloon 1 (G): MFL-HD60CA manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. (Organic balloon (G')) ⁇ Organic balloon 2 (G'): MFL-81GCA manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.
• Antioxidant (F) Antioxidant (F): Clariant piece hindered phenolic antioxidant, HOSTANOX O3 (Antioxidant (F')) ⁇ Antioxidant (F'): BASF hindered phenol antioxidant, IRGANOX1010 (Ultraviolet absorber) ⁇ BASF benzotriazole UV absorber, Tinuvin326 (light stabilizer) ⁇ Light stabilizer 1: BASF HALS, Tinuvin770 ⁇ Light stabilizer 2: HALS manufactured by ADEKA, LA-63P (Dehydrating agent (E)) ⁇ Momentive vinyl silane, A-171 (Adhesion imparting agent) Aminosilane, A-1120 from Momentive (Curing catalyst) ⁇ Nitto Kasei tin catalyst, U220H [Measurement and evaluation method] Measurements and evaluations in Examples and Comparative Examples were carried out by the following methods.
• Each curable composition shown in Table 1 was cured at 23° C./50% RH ⁇ 3 days+50° C. ⁇ 4 days to prepare a sheet having a thickness of about 3 mm.
• a square having a side of 20 mm was cut out of the cured sheet and immersed in hot water at 70° C. for 7 days. After that, the sheet was taken out and tested for weather resistance and humidity resistance for 14 days with a metal weather tester manufactured by Daipla-Wintes.
• the test illuminance was 130 W/m 2
• the black panel temperature during irradiation was 80° C.
• the humidity 50%.
• the curable composition shown in Table 1 was molded into a shape having a width of 10 cm, a length of 10 cm and a thickness of 1 cm, and cured at 23° C. and 50% RH for 7 days.
• An experimental hot plate (NEO HOTPLATE HI-1000, manufactured by AS ONE) is heated to 80 ° C., a cured sample is placed on it, and an infrared radiation thermometer (SK-8700II, manufactured by Sato Keiki Seisakusho) is set after 3 minutes. was used to measure the surface temperature. Evaluation criteria are as follows. Good: The temperature rise compared to the air temperature before measurement is 25°C or less. x: The temperature rise compared with the air temperature before measurement is more than 25 degreeC.
• Synthesis example 1 (Preparation of polymer (A1-1)) Polyoxypropylene glycol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 27,900 having hydroxyl groups at both ends (terminal group equivalent molecular weight of 17,700 ), and polyoxypropylene (P-1) having a molecular weight distribution Mw/Mn of 1.21 was obtained.
• 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. It was found that the polymer (Q-1) had an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal.
• polyoxypropylene (Q-2) having an allyl group at its end was obtained.
• Q-2 polyoxypropylene
• a platinum divinyldisiloxane complex solution 3% by weight isopropanol solution in terms of platinum
• dimethoxymethylsilane was slowly added dropwise while stirring.
• unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a polyoxypropylene (A2 -1) was obtained. It was found that the polymer (A2-1) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 1.4 dimethoxymethylsilyl groups per molecule.
• a 28% methanol solution of sodium methoxide was added in an amount of 1.2 molar equivalents relative to the hydroxyl groups of the obtained polymer (P-6). After methanol was distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of polymer (P-6) to convert terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The obtained unpurified allyl group-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and then the water was removed by centrifugation. Metal salts were removed.
• polyoxypropylene (Q-5) having allyl groups at the terminal sites was obtained.
• this polymer (Q-5) were added 25 mg of a platinum-divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 6.8 g of dimethoxymethylsilane to carry out a hydrosilylation reaction.
• unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A'2) having a dimethoxymethylsilyl group at the end and a number average molecular weight of 19,000. rice field. It was found that the polymer (A'2) had an average of 1.6 dimethoxymethylsilyl groups.
• the resulting curable composition was filled into aluminum cartridges.
• Low modulus, high strength, high elongation, resistance to paint contamination, storage stability, resistance to weathering and humidity, recovery rate, and heat insulating properties were evaluated using the obtained curable composition and its cured product.
• Table 1 shows the results.
• the amount of each component is shown in parts by weight.
• Example 2 200 parts by weight of colloidal calcium carbonate (C1) was changed to 50 parts by weight of colloidal calcium carbonate (C2), the amount of ground calcium carbonate (D) was changed to 250 parts by weight, and the amount of pigment was changed to 10 parts by weight.
• Example 1 except that the antioxidant (F) was changed to the antioxidant (F'), the light stabilizer 2 was changed to the light stabilizer 1, and the amount of the curing catalyst was changed to 1 part by weight.
• a curable composition was obtained in the same manner. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 3 A curable composition was obtained in the same manner as in Example 2, except that the antioxidant (F') was changed to the antioxidant (F). Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 4 A curable composition was obtained in the same manner as in Example 1, except that the organic balloon 1 (G) was not added. Low modulus, high strength, high elongation, resistance to paint contamination, storage stability, resistance to weathering and humidity, recovery rate, and heat insulating properties were evaluated using the obtained curable composition and its cured product. Table 1 shows the results.
• Example 5 Change polymer (A1-1) to 90 parts by weight of polymer (A1-2), change the amount of polymer (A2-1) to 10 parts by weight, and do not add organic balloon 1 (G). Except for this, in the same manner as in Example 1, a curable composition was obtained. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 6 Change the amount of polymer (A1-1) to 95 parts by weight, change polymer (A2-1) to 5 parts by weight of polymer (A2-2), and do not add organic balloon 1 (G). Except for this, in the same manner as in Example 1, a curable composition was obtained. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 7 Change the amount of polymer (A1-1) to 90 parts by weight, change polymer (A2-1) to 10 parts by weight of polymer (A2-2), and do not add organic balloon 1 (G). Except for this, in the same manner as in Example 1, a curable composition was obtained. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 8 Example 1 except that the amount of polymer (A1-1) was changed to 30 parts by weight, the amount of polymer (A2-1) was changed to 70 parts by weight, and organic balloon 1 (G) was not added.
• a curable composition was obtained in the same manner. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 1 A curable composition was obtained in the same manner as in Example 1, except that the amount of the polymer (A1-1) was changed to 100 parts by weight and the polymer (A2-1) was not added. Table 1 shows the results of low modulus, high strength, high elongation, resistance to paint staining, resistance to weathering and humidity, recovery rate, and heat insulating properties of the resulting curable composition and its cured product.
• Example 2 A curable composition was obtained in the same manner as in Example 1, except that the amount of the polymer (A2-1) was changed to 100 parts by weight and the polymer (A1-1) was not added. Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 3 A curable composition was obtained in the same manner as in Example 1, except that the polymers (A1-1) and (A2-1) were changed to 100 parts by weight of the polymer (A2-2). Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 4 A curable composition was obtained in the same manner as in Example 1, except that the polymers (A1-1) and (A2-1) were changed to 100 parts by weight of the polymer (A'1). Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weather and humidity, and heat insulation were evaluated using the resulting curable composition and its cured product. Table 1 shows the results.
• Example 5 A curable composition was obtained in the same manner as in Example 1, except that the polymers (A1-1) and (A2-1) were changed to 100 parts by weight of the polymer (A'2). Low modulus, high strength, high elongation, resistance to paint contamination, resistance to weathering and humidity, recovery rate, and heat insulating properties were evaluated using the obtained curable composition and its cured product. Table 1 shows the results.
• a curable composition was obtained in the same manner as in Example 1, except that the amount of was changed to 3 parts by weight. Low modulus, high strength, high elongation, resistance to paint contamination, storage stability, resistance to weathering and humidity, recovery rate, and heat insulating properties were evaluated using the obtained curable composition and its cured product. Table 1 shows the results.
• Table 1 shows that Examples 1-8 achieve low modulus, high strength, and high elongation compared to Comparative Examples 1-6. That is, Examples 1 to 8 in which two types of polyoxyalkylene-based polymers are combined are more modulus, strength, and elongation at break than Comparative Examples 1 to 6 containing one type of polyoxyalkylene-based polymer, It was found to have excellent properties.
• This curable composition contains a large amount of filler such as calcium carbonate and has excellent physical properties such as low modulus, high strength, and high elongation. can be used for

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