JP2011063669A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide one-component type curable composition that uses an organic polymer containing a reactive silicon group, has excellent workability and is cured to develops high strength. <P>SOLUTION: The curable composition comprises (A) an organic polymer that has a number-average molecular weight of >6,000 and ≤100,000 and contains a reactive silicon group, (B) an organic polymer that has a number-average molecular weight of 500-6,000 and contains a reactive silicon group and (C) silica. The component (A) is an organic polymer having the number-average molecular weight of 6,000-100,000 and containing one or more silicon-containing group represented by general formula (1): -SiR<SP>1</SP><SB>3-a</SB>Z<SB>a</SB>on the terminal and/or side chain of main chain per molecule on the average. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. The present invention relates to a one-component curable composition containing

  The present invention relates to a curable composition comprising an organic polymer containing a reactive silicon group that is useful as a sealing material, an adhesive, an injection material, a putty material, and the like.

  An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have an interesting property of being obtained.

  Among these polymers having reactive silicon groups, polyoxyalkylene polymers and polyisobutylene polymers are disclosed in (Patent Document 1), (Patent Document 2), etc., and are already industrially produced. And widely used in applications such as sealing materials, adhesives, and paints.

  Among these uses, there are uses such as sealing materials and adhesives that require high strength, and it is known to use silica for the purpose of reinforcing effects. (Patent Literature 3), (Patent Literature 4), and (Patent Literature 5) disclose examples of blending silica together with a polymer for the purpose of reinforcing effect.

  However, when silica is added to the polymer as a filler for the purpose of reinforcing, there is a problem that the viscosity of the curable composition is increased and workability is lowered.

JP-A-52-73998 JP-A 63-6041 JP 2000-38560 A JP 2002-37969 A JP 2003-313421 A

  The present invention relates to an organic polymer having a reactive silicon group, an organic polymer containing a reactive silicon group having a number average molecular weight of less than 6000, and a curable composition using silica as a filler, and has good workability. An object of the present invention is to provide a one-component curable composition that exhibits a high strength.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, silica is added to an organic polymer containing a reactive silicon group and an organic polymer containing a reactive silicon group having a number average molecular weight of less than 6000. Has been found to be effective, and the present invention has been completed.

That is, the present invention
1).
(A) an organic polymer containing a reactive silicon group having a number average molecular weight of more than 6,000 and not more than 100,000, and (B) an organic weight containing a reactive silicon group having a number average molecular weight of 500 to 6,000. Coalescence, (C) a curable composition characterized by containing silica,
2).
At the end of the main chain and / or the side chain of the component (A), the general formula (1):
^{_{-SiR 1 3-a Z a (}} 1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3), the curable composition according to 1), which is an organic polymer having an average of one or more silicon-containing groups per molecule,
3).
The curable composition according to 2), wherein Z in the general formula (1) is an alkoxy group,
4).
The organic polymer as the component (A) is an organic polymer having at least one main chain skeleton selected from the group consisting of a polyoxyalkylene polymer and a (meth) acrylate polymer 1) To 3), the curable composition according to any one of
5).
In the main chain skeleton, the organic polymer as the component (A) has the general formula (2):
—NR ² —C (═O) — (2)
(R ² represents a hydrogen atom or a substituted or unsubstituted organic group), and the curable composition according to any one of 1) to 4),
6).
The number average molecular weight of the organic polymer as the component (B) is in the range of 500 to 3,000, and at the end of the main chain and / or the side chain, the general formula (1):
^{_{-SiR 1 3-a Z a (}} 1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3), and is an organic polymer having an average of one or more silicon-containing groups represented by one molecule per 1) to 5) A curable composition of
7).
(C) The curable composition according to any one of 1) to 6), wherein the component is synthetic amorphous silica,
8).
(C) The curable composition according to 7), wherein the component is hydrophilic silica,
9).
(C) The curable composition according to 7), wherein the component is hydrophilic silica synthesized by a wet method,
10).
(C) The curable composition according to 7), wherein the component is hydrophilic silica synthesized by a dry method,
About.

  The one-component curable composition of the present invention has good workability, and the cured composition exhibits high strength.

  The present invention will be described in detail below.

  In the present invention, an organic polymer having a reactive silicon group is used as the component (A) and the component (B).

  The main chain skeleton of the organic polymer (A) having a reactive silicon group used in the present invention and the organic polymer (B) having a reactive silicon group other than the component (A) is not particularly limited. You can use one with

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product Is more preferable because of its excellent cold resistance.

  The glass transition temperature of the organic polymer which is the component (A) or the component (B) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. It is particularly preferred. If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease. The glass transition temperature is a value obtained by DSC measurement.

  In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-component composition, and also in excellent adhesiveness. A polyoxyalkylene polymer is most preferred.

The reactive silicon group contained in the organic polymer having a reactive silicon group has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is a group that can be crosslinked by. As the reactive silicon group, the general formula (1):
^{_{-SiR 1 3-a Z a (}} 1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3).

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, 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. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  Hydrolyzable groups and hydroxyl groups can be bonded to the silicon atom in the range of 1 to 3, and when two or more bonds are bonded to the silicon group, they may be the same or different. Good.

Specific examples of R ¹ include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, R ′ is a methyl group, Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— which is a phenyl group. Of these, a methyl group is particularly preferred.

  More specific examples of reactive silicon groups include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, methoxydimethylsilyl. Group, ethoxydimethylsilyl group and the like. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because of high activity and good curability. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. The triethoxysilyl group is particularly preferred because the alcohol produced in the hydrolysis reaction of the reactive silicon group is ethanol, which has higher safety.

  In addition, an organic polymer having a reactive silicon group having three hydrolyzable groups on a silicon atom provides a high curability, and also has a good restorability, durability, and creep resistance. This is preferable.

  Introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method is mentioned.

  (B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Subsequently, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

  (B) An organic polymer containing an unsaturated group obtained in the same manner as in the method (a) is reacted with a compound having a mercapto group and a reactive silicon group.

  (C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  Among the above methods, the method (a) or the method (c) in which the organic polymer having a hydroxyl group at the terminal is reacted with the compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. It is preferable because a high conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxymate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the obtained organic polymer has high curability, storage stability, elongation characteristics, and tensile strength.

Among the hydrosilane compounds, the general formula (3):
H-SiZ ₃ (3)
The hydrosilane compound represented by the formula (wherein Z is the same as described above) is preferable because the curability of the curable composition made of an organic polymer obtained by the addition reaction of the hydrosilane compound is excellent. Among the hydrosilane compounds represented by the general formula (3), trialkoxysilanes such as trimethoxysilane, triethoxysilane, and triisopropoxysilane are more preferable.

Among the trialkoxysilanes, a trialkoxysilane having an alkoxy group having 1 carbon atom (methoxy group) such as trimethoxysilane may proceed rapidly, and the disproportionation reaction proceeds. This produces a rather dangerous compound such as dimethoxysilane. From the viewpoint of safety in handling, the general formula (4):
H-Si (OR ³ ) ₃ (4)
It is preferable to use a trialkoxysilane having an alkoxy group having 2 or more carbon atoms represented by the formula (wherein three R ³ are each independently an organic group having 2 to 20 carbon atoms). From the viewpoint of availability and safety in handling, triethoxysilane is most preferable.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyldiethoxymethyl. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  Examples of the method of reacting the organic polymer having a hydroxyl group at the terminal with the compound having an isocyanate group and a reactive silicon group in the synthesis method (c) include the method described in JP-A-3-47825. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyldimethoxymethylsilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyldiethoxymethyl. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  As described above, a disproportionation reaction may proceed in a silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane. As the disproportionation reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups such as trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthesis method (b) or (c) may be used. preferable.

  The organic polymer having a reactive silicon group as component (A) may be linear or branched, and its number average molecular weight is more than 6,000 and not more than 100,000 in terms of polystyrene in GPC. More preferably, it is 7,000-50,000, Most preferably, it is 9,000-30,000. When the number average molecular weight is 6000 or less, there is an inconvenient tendency in terms of elongation characteristics of the cured product, and when it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  The organic polymer having a reactive silicon group other than the component (A), which is the component (B), may have a straight chain shape or a branched structure, and its number average molecular weight is 500 to 6000 in terms of polystyrene in GPC. , Preferably less than 6,000, more preferably less than 5,000, and particularly preferably less than 3,000. When the number average molecular weight is 6,000 or more, the viscosity of the curable composition is increased, which tends to be inconvenient in terms of workability. When the number average molecular weight is less than 3,000, the viscosity of the curable composition is low, and the workability tends to be good. A number average molecular weight of less than 500 is not preferable because of a decrease in the elongation of the cured product.

  In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the reactive silicon groups contained in both the organic polymer (A) component and the (B) component are averaged in one molecule of the polymer. And at least 1, preferably 1.1-5. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.

The polyoxyalkylene polymer essentially has the general formula (5):
-R ⁴ -O- (5)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ in the general formula (5) is the number of carbon atoms. 1 to 14, more preferably 2 to 4, linear or branched alkylene groups are preferred. Specific examples of the repeating unit represented by the general formula (5) include

Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or has a relatively low viscosity.

  Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

  A method for producing a polyoxyalkylene polymer having a reactive silicon group is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, JP-A-57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Killen polymer can be exemplified, but not particularly limited thereto.

  The above polyoxyalkylene polymers having a reactive silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. The main monomer is an olefin compound having 2 to 6 carbon atoms, or (2) a diene compound such as butadiene or isoprene is homopolymerized, or is copolymerized with the olefin compound. After that, it can be obtained by a method such as hydrogenation. However, the isobutylene polymer and the hydrogenated polybutadiene polymer can easily introduce a functional group at the terminal, easily control the molecular weight, The number can be increased, and an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. What contains more than weight% is preferable, What contains 80 weight% or more is more preferable, What contains 90 to 99 weight% is especially preferable.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

  Examples of the method for producing a saturated hydrocarbon polymer having a reactive silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The saturated hydrocarbon polymer having a reactive silicon group may be used alone or in combination of two or more.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, (meth) acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In applications such as general construction, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, since the good oil resistance is impaired as the proportion of butyl acrylate is increased, the proportion is preferably 40 mol% or less, more preferably 30 mol% for applications requiring oil resistance. More preferably, it is as follows. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio is preferably 40 mol% or less when heat resistance is required. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30/30 to 20). In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. .

  It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to carry out by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a large degree of freedom in designing initiators and catalysts ( The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive silicon group include chain transfer described in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. A production method using a free radical polymerization method using an agent is disclosed. Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

  The (meth) acrylic acid ester-based polymer having a reactive silicon group may be used alone or in combination of two or more.

  These organic polymers having a reactive silicon group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, and a (meth) acrylic acid ester polymer having a reactive silicon group An organic polymer obtained by blending two or more selected from the above can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto. A preferred specific example has a reactive silicon group and a molecular chain substantially having the following general formula (6):
—CH ₂ —C (R ⁵ ) (COOR ⁶ ) — (6)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkyl group having 1 to 8 carbon atoms) and a (meth) acrylate ester having an alkyl group having 1 to 8 carbon atoms A monomer unit and the following general formula (7):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (7)
(Wherein, R ⁵ is the same as above, and R ⁷ represents an alkyl group having 10 or more carbon atoms) represented by a (meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms And a copolymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group.

R ^{6 in the} general formula (6) is, for example, 1 to 8, preferably 1 to 4, carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, and 2-ethylhexyl group. More preferred are 1 or 2 alkyl groups. The alkyl group of R ⁶ may alone, or may be a mixture of two or more.

R ^{7 in the} general formula (7) is, for example, a long chain having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10 to 30, preferably 10 to 20 And an alkyl group. The alkyl group R ⁷ may alone, or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (6) and (7). The term “substantially” as used herein refers to the copolymer. It means that the total of the monomer units of the formula (6) and the formula (7) present therein exceeds 50% by weight. The total of the monomer units of the general formula (6) and the general formula (7) is preferably 70% by weight or more.

  The ratio of the monomer unit of the general formula (6) to the monomer unit of the general formula (7) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, by weight. .

  Examples of monomer units other than the general formula (6) and general formula (7) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, and N-methylol. Monomers containing amide groups such as acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and nitrogen-containing groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α -Monomer units derived from methyl styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  Organic polymers obtained by blending a saturated hydrocarbon polymer having a reactive silicon group and a (meth) acrylic acid ester copolymer having a reactive silicon group are disclosed in JP-A-1-168774 and JP-A-2000-. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a reactive silicon functional group, in the presence of an organic polymer having a reactive silicon group, A method of polymerizing a (meth) acrylic acid ester monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  On the other hand, the main chain skeleton of the organic polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

  Although it does not specifically limit as said urethane bond component, The group (henceforth an amide segment) produced | generated by reaction of an isocyanate group and an active hydrogen group can be mentioned.

The amide segment has the general formula (2):
—NR ² —C (═O) — (2)
(R ² represents a hydrogen atom or a substituted or unsubstituted organic group).

  Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (2).

An example of an industrially easy production method of an organic polymer having an amide segment and a reactive silicon group is as follows. An organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to produce a polyurethane-based main polymer. After forming a polymer having an isocyanate group at the chain end, or at the same time, all or a part of the isocyanate group may be represented by the general formula (8)
_{^{W-R 8 -SiR 1 3-}} a Z a (8)
(In the formula, R ¹ , Z and a are the same as above. R ⁸ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an unsubstituted or monosubstituted amino group. Things can be mentioned. Examples of known production methods for organic polymers related to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), Japanese Patent Application Laid-Open No. Sho 62. No. 13430 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21879 (US) (Japanese Patent No. 5364955), Japanese Patent Laid-Open No. 10-53637 (US Pat. No. 5,757,751), Japanese Patent Laid-Open No. 11-100197, Japanese Patent Laid-Open No. 2000-169544, Japanese Patent Laid-Open No. 2000-169415, Japanese Patent Laid-Open No. 2002-212415, and Japanese Patent No. 3313360 , US Pat. No. 4,067,844, US Pat. No. 37 No. 1445, JP 2001-323040, and the like.

Further, the organic polymer having an active hydrogen-containing group at the terminal is represented by the general formula (9)
O = C = N—R ⁸ —SiR ¹ _3−a Z _a (9)
(However, in the formula, R ¹ , R ⁸ , Z, and a are the same as above.) Those produced by reacting with a reactive silicon group-containing isocyanate compound can be mentioned. Examples of known production methods of organic polymers related to this production method include JP-A Nos. 11-279249 (US Pat. No. 5,990,257), JP-A No. 2000-119365 (US Pat. No. 6,046,270), and JP-A No. 58-. No. 29818 (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155138, JP-A-2002-249538, WO03 / 018658, WO03 / 059981 Etc.

  Examples of the organic polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxyl group at the terminal (polyolefin polyol). ), Polythiol compounds, polyamine compounds and the like. Among these, polyether polyol, polyacryl polyol, and polyolefin polyol are preferable because the obtained organic polymer has a relatively low glass transition temperature and the resulting cured product is excellent in cold resistance. In particular, polyether polyols are particularly preferred because the resulting organic polymer has low viscosity, good workability, and good deep part curability. Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the resulting cured organic polymer has good weather resistance and heat resistance.

  As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxyl groups per molecular terminal in terms of the total molecular average are preferred. Specifically, an alkylene oxide produced by using a conventional alkali metal catalyst, an initiator such as a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex or cesium, and an alkylene oxide. An oxyalkylene polymer produced by reacting with oxyalkylene.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex has a lower degree of unsaturation, a smaller Mw / Mn, a lower viscosity, a high acid resistance, and a high weather resistance oxyalkylene heavy. It is preferable because a coalescence can be obtained.

  Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure. Specific examples include UH-2000 manufactured by Toagosei Co., Ltd.

  Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .

  Although there is no limitation in particular as a silicon compound of General formula (8), when it illustrates concretely, (gamma) -aminopropyl trimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyl trimethoxysilane, (gamma)-( Amino such as N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; and the like. JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), JP-A 2000-169544, JP-A 2000-169545. As described in the above, Michael addition reaction product of various α, β-unsaturated carbonyl compounds and amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds. Michael addition reactants can also be used as silicon compounds of general formula (8).

  The reactive silicon group-containing isocyanate compound of the general formula (9) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like. Further, as described in JP-A-2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of the general formula (8) with an excess of the polyisocyanate compound is also represented by the general formula: It can be used as the reactive silicon group-containing isocyanate compound (9).

  When there are many amide segments in the main chain skeleton of the organic polymer which is the component (A) or component (B) of the present invention, the viscosity of the organic polymer tends to increase. Moreover, a viscosity may rise after storage and workability | operativity of the composition obtained may fall. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferable that the amide segment is not substantially contained. On the other hand, the amide segment in the main chain skeleton of the component (A) and the component (B) tends to improve the curability of the composition of the present invention. Therefore, when the main chain skeleton of the component (A) and the component (B) includes an amide segment, the average number of amide segments is preferably 1 to 10, more preferably 1.5 to 7, more preferably 2 per molecule. ~ 5 are particularly preferred. When the number is less than 1, the curability may not be sufficient, and when the number is more than 10, the organic polymer may have a high viscosity, resulting in a poor workability composition.

Further, among the organic polymers produced by the above method using the compound of the general formula (8) or the general formula (9), an organic polymer comprising a compound in which R ⁸ is —CH ₂ — Excellent curability tends to be obtained.

  Such component (B) is usually used in a range of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, per 100 parts by weight of component (A). When the amount of component (B) used is less than 10 parts by weight, the viscosity of the composition may be too high, and when it exceeds 50 parts by weight, the elongation of the cured product may decrease, which is not preferred.

  In the present invention, silica is used as the component (C).

  Silica is roughly classified into surface-treated silica obtained by reacting silanol groups on the silica surface with various chemical substances and untreated silica called hydrophilic silica that does not chemically modify silanol groups. Untreated silica has excellent compatibility with polar molecules such as water because silanol groups having strong affinity with water are present on the entire surface of the silica. For this reason, it is called hydrophilic silica.

  On the other hand, surface-treated silica is synthesized by reacting surface silanol of hydrophilic silica with organic halogen, alcohol, silane coupling agent, or the like. By treating the synthesized surface-treated silica, the density of silanol groups is lowered and the amount of moisture adsorption is also reduced. Further, the surface polarity is greatly changed by the surface treatment agent, and the compatibility with the polymer to be filled is greatly changed. Surface-treated silica that exhibits hydrophobicity compared to hydrophilic silica is called hydrophobic silica.

  Hydrophilic silica and hydrophobic silica are used for filling liquids, polymers, elastomer thickeners, thixotropic agents, reinforcing agents, and the like. In terms of cost, hydrophobic silica is more expensive than hydrophilic silica. However, the surface is inactivated, it does not react with other fillers during storage, it is easy to stabilize, and it is difficult to absorb moisture. Used for elastomer products. Also in the curable composition, hydrophobic silica is generally recommended as a filler.

  Silica can be categorized according to various criteria other than the presence or absence of surface treatment. There are various standards such as natural or synthetic products, types of manufacturing methods, crystalline or non-crystalline.

  Synthetic and amorphous silica is called synthetic amorphous silica and is used for various purposes as a functional filler.

  Synthetic amorphous silica is roughly classified into dry process silica and wet process silica.

  Dry silica is generally synthesized from silicon tetrachloride as a raw material, and silanes such as tritylchlorosilane and trichlorosilane are used as a raw material either alone or mixed with silicon tetrachloride. These raw materials are vaporized and subsequently react quantitatively with water produced as an intermediate in an acid / hydrogen gas flame to form the desired silica.

  Dry silica does not have siloxane bonds between primary particles, and the aggregate structure is caused by hydrogen bonds or van der Waals forces and does not form secondary particles. Moreover, since it produces | generates at high temperature (1000 to 1200 degreeC), there are few silanol groups. Therefore, dry silica is dispersed in the vicinity of primary particles by shearing, has few silanol groups, and has little moisture adhering to it, so it is used in the field of functional rubber materials that emphasize low foaming, high transparency, and reinforcement. ing. On the other hand, wet-process silica is usually synthesized by reacting sodium silicate with a mineral acid (typically sulfuric acid).

  Wet process silica has siloxane bonds between primary particles, and its strength depends on the pore volume and the reaction after aggregation at the time of production. Has a particle structure. Wet silica is used for film anti-blocking agents using hard secondary particle structures, rubber applications using soft secondary particles, and the like.

  The amount of silica (C) used is not particularly limited, but is preferably contained in a proportion of 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of component (A) and (B). More preferred is 30 parts by weight or less. If it is less than 5 parts by weight, the reinforcing effect is small, which is not preferable. If it exceeds 50 parts by weight, the viscosity is high and the extrusion property is poor, which is not preferable.

  Various hydrophilic silicas and hydrophobic silicas synthesized by the dry method described above can be purchased from Evonik Co., Ltd., Nippon Aerosil Co., Ltd., and Tokuyama Co., Ltd. Various hydrophilic silicas and hydrophobic silicas synthesized by a wet method can be purchased from Fuji Silysia Co., Ltd., Nippon Silica Industry Co., Ltd., and Tokuyama Co., Ltd.

  The hydrophilic silicas of Evonik Co., Ltd. and Nippon Aerosil Co., Ltd. synthesized by the dry method are, for example, AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600, etc. For example, AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R7200, 00 and the like.

  Examples of the hydrophilic silica of Fuji Silysia Co., Ltd. synthesized by the wet method include Silicia 250, Silicia 350, Silicia 450, Silicia 550, and Silicia 740. For hydrophobic silica, silo-hovic 200 and silo-hovic 704 are used. , Silo hovic 505, silo hovic 603, and the like.

  A silane coupling agent, a curing catalyst, a filler, a thixotropic agent, a plasticizer, a diluent, a stabilizer, a colorant, and the like can be added to the curable composition of the present invention as necessary.

  Specific examples of the silane coupling agent include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxy Amino groups such as silane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane Containing silanes; γ Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ- Epoxy such as glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Group-containing silanes; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxy Halogen-containing silanes such as silane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ- Examples include isocyanate group-containing silanes such as isocyanatepropylmethyldimethoxysilane. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used. These silane coupling agents may be used alone or in combination of two or more.

  Such a silane coupling agent is generally used in the range of 0.5 to 20 parts by weight, preferably in the range of 1 to 15 parts by weight, with respect to 100 parts by weight of the total of the components (A) and (B). Is good. If the silane coupling agent is less than 0.5 parts by weight, the adhesiveness is lowered, and if it exceeds 20 parts by weight, the reactivity of the composition may be lowered. In particular, aminosilane, its reaction product, epoxy silane, and isocyanate silane are preferable from the viewpoint of adhesiveness.

  Specific examples of the curing catalyst include, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, dibutyltin oxide and phthalate ester Reaction products, organotin compounds such as dibutyltin bisacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetra Chelate compounds such as acetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, laurylamine, monoethano Ruamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) Amine compounds such as phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5,4,0] undecene-7 (hereinafter abbreviated as DBU), or of these amine compounds Salt with carboxylic acid, etc .; Acid phosphate ester; Reaction product of acid phosphate ester and amine; Saturated or unsaturated polyvalent carboxylic acid or acid anhydride thereof; Low amount obtained from excess polyamine and polybasic acid Molecular weight polyamide resin; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; Examples of the silanol condensation catalyst include known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.

  Such a curing catalyst is generally used in a range of 0.01 to 15 parts by weight, preferably in a range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the sum of the components (A) and (B). Is good. If it is less than 0.01 part by weight, the curability of the composition is lowered, and if it exceeds 15 parts by weight, storage stability and adhesiveness are lowered. In particular, a tetravalent tin catalyst is preferable from the viewpoint of curing speed and storage stability.

  In the present invention, silica as component (C) is used as a filler. Moreover, fillers other than the component (C) can also be used as the filler. For example, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, fused silica, diatomaceous earth, white clay, kaolin, clay, talc, wood powder, walnut shell powder, rice husk powder, anhydrous silicic acid, quartz powder, aluminum powder, zinc powder , Inorganic fillers such as asbestos, glass fibers, carbon fibers, glass beads, alumina, glass balloons, shirasu balloons, silica balloons, wood fillers such as pulp and cotton chips, powder rubber, recycled rubber, thermoplastic or thermosetting Examples of the organic filler include fine powders of conductive resin and hollow bodies such as polyethylene. These fillers may be used alone or in combination of two or more.

  Such a filler may be used in a range of usually 50 to 1000 parts by weight, preferably 60 to 900 parts by weight with respect to 100 parts by weight of the total of the component (A) and the component (B). When the amount of the filler used is less than 50 parts by weight, the cost of the composition increases, and when it exceeds 1000 parts by weight, the viscosity increases and the workability decreases. In particular, calcium carbonate is preferable in terms of quality and cost.

  Specific examples of the thixotropic agent include hydrogenated castor oil, organic amide wax, organic bentonite, and calcium stearate. These thixotropic agents may be used alone or in combination of two or more.

  Such thixotropic agent is used in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of component (A) and component (B). good. If the amount of the thixotropic agent used is less than 0.1 parts by weight, sufficient thixotropy may not be obtained, and if it exceeds 50 parts by weight, it is not preferable from the viewpoint of cost increase.

  Specific examples of the plasticizer include phthalates such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic dibasic esters such as dioctyl adipate, isodecyl succinate, and dibutyl sebacate; diethylene glycol dibenzoate Glycol esters such as pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetylricinoleate; phosphate esters such as tricresyl phosphate, trioctyl phosphate and octyl diphenyl phosphate, epoxidized soybean oil, epoxy Epoxy plasticizers such as modified linseed oil and epoxy benzyl stearate; polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and derivatives thereof; Li -α- methyl styrene, polystyrenes, such as polystyrene, polybutadiene, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and chlorinated paraffins. These plasticizers may be used alone or in combination of two or more.

  Such a plasticizer may be used in a range of usually 10 to 300 parts by weight, preferably 20 to 250 parts by weight, with respect to 100 parts by weight of the total of component (A) and component (B). When the amount of the plasticizer used is less than 10 parts by weight, the viscosity of the composition may be too high, and when it exceeds 300 parts by weight, the plasticizer may exude from the cured product. Absent.

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

 Such a light stabilizer is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the total of the components (A) and (B). Specific examples of the light stabilizer are also described in JP-A-9-194731.

  An ultraviolet absorber can be added to the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred.

  Such an ultraviolet absorber is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the total of component (A) and component (B). It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

The one-component curable composition of the present invention is prepared as a one-component type in which all the blended components are preliminarily blended and sealed and cured by moisture in the air after construction. Since all the blending components are blended in advance, it is preferable that the blending component containing moisture is used after being dehydrated and dried in advance, or dehydrated by decompression during blending and kneading. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to this dehydration drying method,
Lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- The storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of such a dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). Preferably, 0.5 to 10 parts by weight is more preferable.

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

  When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

  The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. Can be used for etc. Since the hardened | cured material obtained by hardening | curing the curable composition of this invention is excellent in a softness | flexibility and adhesiveness, it is more preferable to use as a sealing material or an adhesive agent among these.

  Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

  In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited thereto.

(Synthesis Example 1)
Polymerization of propylene oxide was carried out using a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a polypropylene oxide having a number average molecular weight of about 19,000. Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As a result, a polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain purified allyl group-terminated polypropylene oxide (P-1).

For 100 parts by weight of the allyl-terminated polypropylene oxide (P-1), 1.40 parts by weight of methyldimethoxysilane and 2 parts at 90 ° C. with 50 ppm of a 2-propanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. The reaction was performed for a time to obtain a methyldimethoxysilyl group-terminated polypropylene oxide (A-1). ^According to measurement by ¹ H-NMR, the average number of terminal methyldimethoxysilyl groups was about 2.3 per molecule.

(Synthesis Example 2)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. Polypropylene oxide having a number average molecular weight of about 19,000 was obtained. Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As a result, a polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain purified allyl group-terminated polypropylene oxide (P-2).

With respect to 100 parts by weight of the obtained allyl-terminated polypropylene oxide (P-2), 50 ppm of 2-propanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst and 1.35 parts by weight of methyldimethoxysilane and 2 at 90 ° C. The reaction was carried out for a period of time to obtain methyldimethoxysilyl group-terminated polypropylene oxide (A-2). ^{As a} result of measurement by ¹ H-NMR, the number of terminal methyldimethoxysilyl groups averaged about 1.7 per molecule.

(Synthesis Example 3)
Add 1.2 times equivalent NaOMe methanol solution to the hydroxyl group of polyoxypropylene diol having a number average molecular weight of about 3,000 to distill off the methanol, and then add allyl chloride to convert the terminal hydroxyl group to an allyl group. Converted to. Thus, polypropylene oxide having a number average molecular weight of about 3,000 having an allyl group at the end was obtained. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain purified allyl group-terminated polypropylene oxide (P-3).

With respect to 100 parts by weight of the obtained allyl-terminated polypropylene oxide (P-3), 50 ppm of 2-propanol solution containing 3 wt% of platinum in a platinum vinylsiloxane complex as a catalyst and 6.00 parts by weight of methyldimethoxysilane at 90 ° C. The reaction was performed for a time to obtain a methyldimethoxysilyl group-terminated polypropylene oxide (B-1). ^{As a} result of measurement by ¹ H-NMR, the number of terminal methyldimethoxysilyl groups averaged about 1.5 per molecule.

(Examples 1 and 2)
Surface treated colloidal calcium carbonate shown in Table 1 with respect to a total of 100 parts by weight of the organic polymer (A-1) obtained in Synthesis Example 1 and the organic polymer (B-1) obtained in Synthesis Example 3. (Manufactured by Maruo Calcium Co., Ltd., trade name: Calfine 200M), 50 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Whiteon SB), hydrophilic silica (manufactured by Nippon Aerosil Co., Ltd.) 20 parts by weight of product name: AEROSIL200) and 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Typek R-820) were used, and 40 parts by weight of plasticizer DIDP (diisodecyl phthalate) 2 parts by weight of a modifying agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 326), (Manufactured by Sankyo Co., trade name: Sanol LS770) stabilizer using 1 part by weight, was thoroughly kneaded by mixing the various formulations were dispersed through once in a ceramic three-roll paint mill. Then, after drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, 3 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and as an adhesion-imparting agent 5 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120), γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Co., Ltd.) (Product name: A-187) 2 parts by weight were added, and further sufficiently stirred. Finally, a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Example 3)
Surface treated colloidal calcium carbonate shown in Table 1 with respect to a total of 100 parts by weight of the organic polymer (A-1) obtained in Synthesis Example 1 and the organic polymer (B-1) obtained in Synthesis Example 3. (Manufactured by Maruo Calcium Co., Ltd., trade name: Calfine 200M), 75 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Whiteon SB), 25 parts by weight of hydrophilic silica (manufactured by Nippon Aerosil Co., Ltd.) 20 parts by weight of product name: AEROSIL200) and 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Typek R-820) were used, and 40 parts by weight of plasticizer DIDP (diisodecyl phthalate) 2 parts by weight of a modifying agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 326), (Manufactured by Sankyo Co., trade name: Sanol LS770) stabilizer using 1 part by weight, was thoroughly kneaded by mixing the various formulations were dispersed through once in a ceramic three-roll paint mill. Then, after drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, 3 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and as an adhesion-imparting agent 5 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120), γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Co., Ltd.) (Product name: A-187) 2 parts by weight were added, and further sufficiently stirred. Finally, 1 part by weight of a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Comparative Example 1)
With respect to 100 parts by weight of the organic polymer (A-1) obtained in Synthesis Example 1, 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Baiyinhua CCR) shown in Table 1 And 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Taipei P-820), 55 parts by weight of plasticizer DIDP (diisodecyl phthalate), thixotropic agent (manufactured by Enomoto Kasei Co., Ltd.) , Trade name: Disparon # 6500) 2 parts by weight, UV absorber (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 327) 1 part by weight, light stabilizer (Sankyo Co., Ltd., trade name: Sanol) LS770) 1 part by weight was used, and various blends were mixed and sufficiently kneaded, and then passed once through a ceramic three paint roll and dispersed. Thereafter, drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, and 2 parts by weight of vinyltrimethoxysilane (product name: A-171) as a dehydrating agent, as an adhesion-imparting agent. 3 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120) was added, and the mixture was further stirred sufficiently. Finally, 2 parts by weight of a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Comparative Example 2)
With respect to 100 parts by weight of the organic polymer (A-2) obtained in Synthesis Example 2, 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Baiyinhua CCR) shown in Table 1; And 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Tycop R-820), 55 parts by weight of plasticizer DIDP (diisodecyl phthalate), thixotropic agent (manufactured by Enomoto Kasei Co., Ltd.) , Trade name: Disparon # 6500) 2 parts by weight, UV absorber (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 327) 1 part by weight, Light stabilizer (Sankyo Co., Ltd., trade name: Sanol) LS770) 1 part by weight was used, and various blends were mixed and sufficiently kneaded, and then passed once through a ceramic three paint roll and dispersed. Then, after drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or less, 2 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and as an adhesion promoter. 3 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120) was added, and the mixture was further stirred sufficiently. Finally, 2 parts by weight of a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Comparative Example 3)
For 100 parts by weight of the organic polymer (A-1) obtained in Synthesis Example 1, 50 parts by weight of heavy calcium carbonate (Shiraishi Calcium Co., Ltd., Whiten SB) shown in Table 1, hydrophilic silica (Nippon Aerosil Co., Ltd., trade name: AEROSIL200) 20 parts by weight and Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Typek R-820) 20 parts by weight were used. 40 parts by weight of diisodecyl acid), 2 parts by weight of thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500), UV absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 327) 1 1 part by weight, 1 part by weight of a light stabilizer (manufactured by Sankyo Co., Ltd., trade name: Sanol LS770), and after mixing and blending the various compounds, 1 in 3 ceramic paint rolls Through and were dispersed. Then, after drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, 3 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and as an adhesion-imparting agent 5 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120), γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Co., Ltd.) (Product name: A-187) 2 parts by weight were added, and further sufficiently stirred. Finally, 1 part by weight of a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Comparative Example 4)
50 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name: Calfine 200M) shown in Table 1 with respect to 100 parts by weight of the organic polymer (A-1) obtained in Synthesis Example 1. , Heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Whiteon SB) 50 parts by weight, hydrophilic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL 200), and titanium oxide (Ishihara Sangyo Co., Ltd.) Manufactured, trade name: Typaque R-820) 20 parts by weight, plasticizer DIDP (diisodecyl phthalate) 40 parts by weight, thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500) 2 1 part by weight, UV absorber (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 327), light stabilizer (Sankyo Co., Ltd., trade name: Sanol LS7) 0) using 1 part by weight, it was thoroughly kneaded by mixing the various formulations were dispersed through once in a ceramic three-roll paint mill. Then, after drying under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, 3 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and as an adhesion-imparting agent 5 parts by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Mentive Co., Ltd., trade name: A-1120), γ-glycidoxypropyltrimethoxysilane (manufactured by Momentive Co., Ltd.) (Product name: A-187) 2 parts by weight were added, and further sufficiently stirred. Finally, 1 part by weight of a curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added and kneaded. In this way, the curable composition was made substantially free of moisture, sealed in a cartridge which is a moisture-proof container, and sealed to obtain a one-component curable composition.

(Skinning time)
Each curable composition was extruded from the cartridge, filled into a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat surface. This time was taken as the curing start time, and the surface was touched with a spatula every minute, and the time when the compound no longer adhered to the spatula was measured as the skinning time.

(Viscosity of curable composition)
The curable composition was filled in a 100 cc cup so that air did not enter, and the curable composition was 23 ° C. and 50% R.D. H. Under the conditions, the viscosities at 1 rpm, 2 rpm, and 10 rpm were measured using a BS type viscometer manufactured by Tokimec Co., Ltd.

(Mechanical properties of cured product)
The above curable composition is filled into a sheet-like mold having a thickness of 3 mm, the surface is prepared, placed under conditions of 23 ° C. and 50% RH for 3 days, further placed at 50 ° C. for 4 days, after curing and curing, and then a dumbbell form A dumbbell-shaped cured product was made by punching out with Using this dumbbell piece, a tensile test (autograph made by Shimadzu Corporation) was performed at a tensile speed of 200 mm / min, and M50: 50% tensile modulus (MPa), M100: 100% tensile modulus (MPa), TB: Strength at break (MPa) and elongation at break were measured.

  Various evaluation results are shown in Table 1.

  When Examples 1, 2, and 3 are compared with Comparative Examples 1, 2, and 3, the modulus is high in Examples. From this, it can be said that the cured compositions of Examples have high strength.

  When Examples 1, 2, 3 and Comparative Example 4 are compared, the modulus is high in the examples and the viscosity is low in the examples. From this, it can be said that the curable composition of an Example has favorable workability | operativity and the cured composition is high intensity | strength.

Claims (10)

  (A) An organic polymer containing a reactive silicon group having a number average molecular weight of more than 6,000 and not more than 100,000, and (B) containing a reactive silicon group having a number average molecular weight of 500 to 6,000. A curable composition comprising an organic polymer and (C) silica. At the end of the main chain and / or the side chain of the component (A), the general formula (1):
^{_{-SiR 1 3-a Z a (}} 1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3), and is an organic polymer having an average of one or more silicon-containing groups per molecule. .   The curable composition of Claim 2 whose Z of General formula (1) is an alkoxy group.   The organic polymer as component (A) is an organic polymer having at least one main chain skeleton selected from the group consisting of a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer. The curable composition in any one of 1-3. In the main chain skeleton, the organic polymer as the component (A) has the general formula (2):
—NR ² —C (═O) — (2)
The curable composition according to claim 1, which has a group represented by (R ² represents a hydrogen atom or a substituted or unsubstituted organic group). The number average molecular weight of the organic polymer as the component (B) is in the range of 500 to 3,000, and at the end of the main chain and / or the side chain, the general formula (1):
^{_{-SiR 1 3-a Z a (}} 1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3), and is an organic polymer having an average of one or more silicon-containing groups per molecule. Curable composition.   (C) A component is synthetic amorphous silica, The curable composition in any one of Claims 1-6.   The curable composition according to claim 7, wherein the component (C) is hydrophilic silica.   The curable composition according to claim 7, wherein the component (C) is hydrophilic silica synthesized by a wet method. The curable composition according to claim 7, wherein the component (C) is hydrophilic silica synthesized by a dry method.