JP2021161428A - Curable composition and joint structure using it - Google Patents

Abstract

[Problem] To provide a curable composition that has excellent adhesive properties and can maintain excellent rubber elasticity for a long period of time after curing, and a joint structure made using the same. [Solution] The curable composition of the present invention is characterized by containing an organic polymer (I) having a hydrolyzable silyl group, an amine compound (C) having a melting point of 55°C or higher, an aminosilane compound (D), and a silanol condensation catalyst (E). Since the curable composition of the present invention has excellent adhesive properties and can maintain excellent rubber elasticity for a long period of time after curing, it can be used, for example, as a filler for joints formed between exterior wall members that constitute the exterior walls of building structures. [Selected Figure] None

Description

The present invention relates to a curable composition that is cured by moisture in an atmosphere (air) to produce a cured product having excellent weather resistance and adhesiveness.

Conventionally, a curable composition containing an oxyalkylene polymer having a crosslinkable hydrolyzable silyl group has been known (for example, Patent Document 1). In the curable composition, a hydrolyzable silyl group that can be crosslinked by moisture contained in the atmosphere is hydrolyzed and then dehydrated and condensed to produce a cured product having excellent adhesiveness.

As a curable composition, Patent Document 2 discloses a moisture-curable composition containing an organic carboxylate or an organic amine in an alkoxysilyl group-containing polyoxyalkylene polymer.

Such a curable composition is used in, for example, in the outer wall of a building structure, a joint (so-called "joint") between outer wall members such as a mortar plate, a concrete plate, an ALC (Autoclaved Light-weight Concrete) plate, and a metal plate. ) Is used to join the outer wall members to each other. By using the curable composition in this way, it is possible to prevent rainwater from entering the inside of the building structure from the joint between the outer wall members.

In the outer wall of a building structure, the joint width changes slightly because the outer wall member expands or contracts with a temperature change, or the outer wall member moves due to vibration or external force caused by an earthquake or strong wind. Therefore, it is required that the curable composition has excellent rubber elasticity after curing and can be stretchable so that it can firmly adhere to the outer wall and follow the change in joint width.

Japanese Patent No. 5698422 Japanese Unexamined Patent Publication No. 6-16922

However, recently, an outer wall member of a porcelain plate has been preferred because of its design, but there is a problem that a conventional curable composition has low adhesiveness to such an outer wall member. Therefore, when the joint width changes, it becomes difficult for the cured product of the curable composition to expand and contract in accordance with the change in the joint width. In such a case, peeling at the adhesive interface or damage to the outer wall member may occur, causing a problem that rainwater infiltrates into the building structure and causes water leakage. Therefore, it is necessary to improve the adhesiveness of the curable composition.

Further, in the conventional curable composition, after curing, the rubber elasticity decreases with time and becomes hard, and when the joint width changes, it becomes difficult to expand and contract according to the change in the joint width, and the adhesive adheres. There was a problem that peeling occurred at the interface and rainwater infiltrated into the building structure, causing water leakage.

Therefore, an object of the present invention is to provide a curable composition having excellent adhesiveness and capable of maintaining excellent rubber elasticity after curing for a long period of time, and a joint structure using the same. And.

The curable composition of the present invention comprises an organic polymer (I) having a hydrolyzable silyl group, an amine compound (C) having a melting point of 55 ° C. or higher, an aminosilane compound (D), and a silanol condensation catalyst (E). It is characterized by containing.

[Organic polymer (I) having a hydrolyzable silyl group]
The curable composition of the present invention contains an organic polymer (I) having a hydrolyzable silyl group. According to the organic polymer (I) having a hydrolyzable silyl group, it is possible to provide a moisture-curable composition that can be cured by moisture in the atmosphere.

(Polyalkylene oxide (A))
The organic polymer (I) having a hydrolyzable silyl group preferably contains a polyalkylene oxide (A) having a hydrolyzable silyl group. According to the polyalkylene oxide (A), the adhesiveness of the curable composition can be improved.

The polyalkylene oxide (A) has a hydrolyzable silyl group.

The hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom. The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and for example, 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 and a mercapto. Groups, alkenyloxy groups and the like can be mentioned.

As the hydrolyzable silyl group contained in the polyalkylene oxide (A), an alkoxysilyl group is preferable because the hydrolysis reaction is gentle. The alkoxysilyl group includes a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Groups; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group. Of these, a dialkoxysilyl group is more preferable, and a methyldimethoxysilyl group is particularly preferable. According to the polyalkylene oxide (A) having a dialkoxysilyl group, it is possible to provide a curable composition that exhibits excellent rubber elasticity and adhesiveness after curing.

The polyalkylene oxide (A) preferably has 1 to 2 hydrolyzable silyl groups in one molecule on average. When the number of hydrolyzable silyl groups in the polyalkylene oxide (A) is one or more, the curability of the curable composition is improved. Further, when the number of hydrolyzable silyl groups in the polyalkylene oxide (A) is 2 or less, the mechanical strength or extensibility of the cured product of the curable composition is improved. Further, the polyalkylene oxide (A) preferably has a hydrolyzable silyl group at at least one of both ends of the molecular chain.

The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide (A) is the concentration of the hydrolyzable silyl groups in the polyalkylene oxide (A) determined by ^{1 H-NMR, and GPC.} It can be calculated based on the number average molecular weight of the polyalkylene oxide (A) obtained by the method.

As the polyalkylene oxide (A), the main chain has a general formula: _{− (RO) n} − (in the formula, R represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units. A polymer containing a repeating unit represented by (is a positive integer) is preferable. The main clavicle of the polyalkylene oxide may consist of only one repeating unit or may consist of two or more repeating units.

Examples of the main chain skeleton of polyalkylene oxide (A) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Be done. Of these, polypropylene oxide is preferable. According to polypropylene oxide, it is possible to provide a curable composition that exhibits excellent rubber elasticity and adhesiveness after curing.

The number average molecular weight of the polyalkylene oxide (A) is preferably 20,000 to 50,000, more preferably 20,000 to 40,000. When the number average molecular weight of the polyalkylene oxide (A) is 20,000 or more, the rubber elasticity of the cured product of the curable composition is improved. When the number average molecular weight of the polyalkylene oxide (A) is 50,000 or less, the coatability of the curable composition is improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polyalkylene oxide (A) is preferably 1.5 or less, more preferably 1.3 or less, and more preferably 1.0 to 1.3. Preferably, 1.0 to 1.2 is particularly preferable. According to the polyalkylene oxide having a molecular weight distribution of 1.5 or less, the rubber elasticity of the cured product of the curable composition is improved.

In the present invention, the number average molecular weight and the weight average molecular weight of the polyalkylene oxide mean polystyrene-equivalent values measured by the GPC (gel permeation chromatography) method.

Specifically, 6 to 7 mg of polyalkylene oxide is collected, and the collected polyalkylene oxide is supplied to a test tube. A solution of orthodichlorobenzene (o-DCB) containing 0.05% by mass of dibutylhydroxytoluene (BHT) is prepared, and this solution is added to a test tube and diluted so that the concentration of polyalkylene oxide is 1 mg / mL. To prepare a diluted solution. The diluted solution is shaken at 145 ° C. and a rotation speed of 25 rpm for 1 hour using a dissolution filtration device to dissolve the polyalkylene oxide in the solution to prepare a measurement sample. Using this measurement sample, the number average molecular weight and the weight average molecular weight of the polyalkylene oxide can be measured by the GPC method.

The number average molecular weight and the weight average molecular weight of the polyalkylene oxide can be measured by, for example, the following measuring device and measuring conditions.
Measuring device TOSOH product name "HLC-8121GPC / HT"
Measurement conditions Column: TSKgelGMHHR-H (20) HT x 3
TSKguardcolumn-HHR (30) HT x 1
Mobile phase: o-DCB 1.0 mL / min
Sample concentration: 1 mg / mL
Detector: Blythe type refractometer
Standard substance: Polystyrene (Molecular weight manufactured by TOSOH: 500-8420000)
Elution conditions: 145 ° C
SEC temperature: 145 ° C

As the polyalkylene oxide (A) containing a hydrolyzable silyl group, a commercially available one can be used. For example, polyalkylene oxides having a main chain skeleton of polypropylene oxide and having a methyldimethoxysilyl group include product names "Exester S4530", "Exester S6735", and "Exester SAX720" manufactured by AGC Inc. And so on.

(Acrylic polymer (B))
The organic polymer (I) having a hydrolyzable silyl group preferably further contains an acrylic polymer (B) having a hydrolyzable silyl group. According to the acrylic polymer (B), the adhesiveness of the curable composition can be improved. Furthermore, by using the acrylic polymer (B) in combination with the polyalkylene oxide (A) described above, the weather resistance of the curable composition after curing can be improved.

As the hydrolyzable silyl group of the acrylic polymer (B), an alkoxysilyl group is preferable because the cured product of the curable composition can maintain excellent rubber elasticity for a long period of time. .. The alkoxysilyl group includes a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Groups; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group. Of these, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.

As the main chain skeleton of the acrylic polymer (B), a polymer of an acrylic monomer is preferably mentioned. The acrylic monomer has an ethylenically unsaturated double bond, and the weight of the acrylic monomer is added by addition polymerization of such an acrylic monomer in the ethylenically unsaturated double bond. Coalescence is obtained.

Examples of the acrylic monomer in the acrylic polymer (B) include acrylic acid, methacrylic acid, and alkyl (meth) acrylate. Of these, alkyl (meth) acrylate is preferable. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and the like. n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) Examples thereof include acrylate and lauryl (meth) methacrylate. These alkyl (meth) acrylates may be used alone or in combination of two or more. In addition, (meth) acrylate means methacrylate and / or acrylate.

As the main chain skeleton of the acrylic polymer (B), a copolymer of a monomer containing methyl (meth) acrylate and butyl (meth) acrylate is preferable, and a monomer containing methyl methacrylate and butyl acrylate is preferable. Copolymers are more preferred. According to the acrylic polymer (B) in which the main chain skeleton is the above-mentioned copolymer, the tensile-shear adhesive strength of the curable composition after curing can be improved.

In the acrylic polymer (B), the monomer used for the polymer constituting the main chain skeleton may further contain other monomers in addition to the acrylic monomer. Other monomers include, for example, styrenes such as styrene, inden, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene and the like. Derivatives, compounds with vinyl ester groups such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl silicate, maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholin, (meth) ) Acrylonitrile, (meth) acrylamide, N-cyclohexyl maleimide, N-phenyl maleimide, N-lauryl maleimide, N-benzyl maleimide, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether , Cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, butyl benzoate (4-vinyloxy), ethylene glycol divinyl ether, diethylene glycol divinyl ether, Triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol-divinyl ether, diisophthalate ( 4-Vinyloxy) butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyl trimethyl propantrivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane Examples thereof include compounds having a vinyloxy group such as -1,4-dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether. .. These monomers may be used alone or in combination of two or more.

The polymerization method of the acrylic polymer (B) is not particularly limited, and a known method can be used. For example, a free radical polymerization method, an anion polymerization method, a cationic polymerization method, a UV radical polymerization method, and a living anion weight can be used. Various polymerization methods such as legal, living cationic polymerization method, and living radical polymerization method can be mentioned.

The weight average molecular weight of the acrylic polymer (B) is preferably 2,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight of the acrylic polymer (B) is 2,000 or more, thermal deterioration is reduced after curing, and a curable composition capable of maintaining excellent rubber elasticity for a longer period of time is provided. can do. When the weight average molecular weight of the acrylic polymer (B) is 50,000 or less, excellent thread breakability of the curable composition can be ensured, whereby the curable composition can be satisfactorily applied. can.

The weight average molecular weight of the acrylic polymer (B) is a value measured by polystyrene conversion by the GPC (gel permeation chromatography) method. The specific measurement method and measurement conditions are the same as those for measuring the weight average molecular weight of the polyalkylene oxide described above.

The content of the acrylic polymer (B) in the curable composition is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. Parts are more preferable, and 30 to 100 parts by mass are particularly preferable. When the content of the acrylic polymer (B) is 10 parts by mass or more, the photodegradation of the cured product of the curable composition can be reduced and the durability can be improved. When the content of the acrylic polymer (B) is 200 parts by mass or less, the extensibility of the cured product of the curable composition can be improved. As a result, the followability of the cured product to changes in the joint width is improved.

[Amine compound (C)]
The curable composition contains an amine compound (C) having a melting point of 55 ° C. or higher. According to the amine compound (C), it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a long period of time after curing.

The melting point of the amine compound is 55 ° C. or higher, preferably 58 ° C. or higher, more preferably 58 to 100 ° C., and particularly preferably 58 to 90 ° C.

In the present invention, the melting point of the amine compound refers to the temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121 (1987). Specifically, using a differential scanning calorimetry device (for example, device name "DSC-60" manufactured by Shimadzu Corporation), the amine compound is heated from 10 ° C to 150 ° C at a heating rate of 5 ° C / min. Then, the melting peak temperature of the DSC curve in this heating process is defined as the melting point of the amine compound. When there are a plurality of melting peaks, the temperature at the apex of the melting peak having the highest endothermic value is taken as the melting point.

In the present invention, the amine compound (C) means a compound having _{at least one amino group (-NH 2) in one molecule.} The hydrogen atom of the amino group in the amine compound (C) may be substituted with an organic group such as an alkyl group or an aryl group. The amine compound (C) preferably does not have a hydrolyzable silyl group. Further, the amine compound (C) preferably does not contain a silicon atom.

Examples of the amine compound (C) include monoamine compounds, diamine compounds, and triamine compounds. Of these, monoamine compounds and diamine compounds are preferable, and diamine compounds are more preferable.

Preferred examples of the amine compound (C) include a monoamine compound represented by the following formula (1), a diamine compound represented by the following formula (2), and a diamine compound represented by the following formula (3). Among them, the diamine compound represented by the following formula (2) and the diamine compound represented by the following formula (3) are preferable, and the diamine compound represented by the following formula (2) is more preferable.
R ¹ −NH ₂ (1)
R ^2- NH-R ^3- NH ₂ (2)
NH _2- R ^4- NH ₂ (3)
(In the formula (1), R ¹ is a linear or branched alkyl group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group. In the formula (2), R ² is a direct chain. It is a chain or branched alkyl group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group, and R ³ is an alkylene group. In the formula (3), R ⁴ is an alkylene group. .)

In the monoamine compound represented by the formula (1), the ^{number of carbon atoms of R 1} is preferably 15 to 35, more preferably 15 to 30, and even more preferably 15 to 25. By setting the carbon number of R ¹ within the above range, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing. As R ¹ , a linear or branched alkyl group is preferably mentioned.

In the diamine compound represented by the formula (2), ^{the total number of carbon atoms of R 2} and R ³ is preferably 15 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. By setting the total carbon number of R ² and R ³ within the above range, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity after curing for a longer period of time. As R ² , a linear or branched alkyl group is preferably mentioned.

In the diamine compound represented by the formula (3), the ^{number of carbon atoms of R 4} is preferably 10 to 40, more preferably 15 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. By setting the carbon number of R ⁴ within the above range, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing.

Specific examples of the amine compound (C) include behenylamine (C ₂₂ H _45- NH ₂ , melting point 63 ° C.), behenyl propylene diamine (C ₂₂ H _45- NH-C ₃ H _6- NH ₂ , melting point 60 ° C.). ), 1,10-Diaminodecane (NH _2- C ₁₀ H _20- NH ₂ , melting point 62 ° C), 1,12-diaminododecane (NH _2- C ₁₂ H _24- NH ₂ , melting point 70 ° C), dioctadecyl Amines ((C ₁₈ H ₃₇ ) _2- NH, melting point 72 ° C.), 1-tetratoriacontanamine (C ₃₄ H _69- NH ₂ , melting point 84 ° C.) and the like can be mentioned. Of these, behenyl propylene diamine, 1,10-diaminodecane, and 1,12-diaminododecane are preferable, and behenyl propylene diamine is more preferable. The amine compound (C) may be used alone or in combination of two or more.

The content of the amine compound (C) in the curable composition is preferably 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. 5 parts by mass is more preferable, and 1 to 3 parts by mass is particularly preferable. When the content of the amine compound (C) is 0.1 parts by mass or more, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a long period of time after curing. When the content of the amine compound (C) is 10 parts by mass or less, the curability of the curable composition is improved.

[Aminosilane compound (D)]
The curable composition comprises the aminosilane compound (D). As the aminosilane compound (D), aminoalkoxysilane is preferably mentioned. Further, as the aminosilane compound (D), an alkoxysilane oligomer which is a hydrolysis condensate of an alkoxysilane containing aminoalkoxysilane is also preferably mentioned. Further, the aminosilane compound (D) contains a silicon atom. The aminosilane compound (D) may be used alone or in combination of two or more.

(Amino Alkoxy Silane)
The aminoalkoxysilane means a compound having at least one amino group-containing functional group in one molecule and having at least two alkoxy groups directly bonded to a silicon atom. The amino group-containing functional group is preferably directly bonded to the silicon atom. The aminoalkoxysilane is preferably a compound having one amino group-containing functional group in one molecule and having three alkoxy groups directly bonded to a silicon atom.

As the amino group-containing functional group, an aminopropyl functional group is preferable because the adhesiveness of the curable composition is improved. Aminopropyl functional groups include − (CH ₂ ) ₃ −NH ₂ , − (CH ₂ ) ₃ −NHR ⁵ , − (CH ₂ ) ₃ −NH (CH ₂ ) ₂ −NH ₂ (3- [N− ( 2- (2-aminoethyl) amino] propyl group) and − (CH ₂ ) _3- NH (CH ₂ ) _2- NH (CH ₂ ) _2- NH ₂ (3-[[2- (2-aminoethylamino)) At least one aminopropyl functional group selected from the group consisting of ethyl] amino] propyl groups) is preferred. As the aminopropyl functional group, − (CH ₂ ) ₃ −NH ₂ and − (CH ₂ ) ₃ −NH (CH ₂ ) ₂ −NH ₂ are more preferable.

-(CH ₂ ) _3-In NHR ⁵ , R ⁵ has an alkyl group having 1 to 18 carbon atoms, a monovalent saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a carbon number of carbon atoms. There are 6 to 12 aryl groups.

Examples of the alkyl group having 1 to 18 carbon atoms in R ^{5 include a linear alkyl group and a branched chain alkyl group.} Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group and an n-decyl group. Examples thereof include an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. As the linear alkyl group, a methyl group, an ethyl group and an n-butyl group are preferable. Examples of the branched-chain alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

Examples of the monovalent saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms in R ⁵ include a cyclopentyl group, a cycloheptyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a cyclooctyl group and the like. , Cyclohexyl group is preferred.

Examples of the aryl group having 6 to 12 carbon atoms in R ⁵ include a phenyl group and a benzyl group, and a phenyl group is preferable.

Specific examples of the aminoalkoxysilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-aminopropyltrimethoxysilane, N-methyl-aminopropyltriethoxysilane, and Nn. -Butyl-aminopropyltrimethoxysilane, Nn-butyl-aminopropyltriethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-cyclohexylaminopropyltriethoxysilane, N-phenyl-aminopropyltrimethoxysilane, N -Phenyl-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltriethoxysilane, [3- [2] -(2-Aminoethylamino) ethylamino] propyl] trimethoxysilane, [3- [2- (2-aminoethylamino) ethylamino] propyl] triethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-amino Propylmethyldiethoxysilane, N-methyl-aminopropylmethyldimethoxysilane, N-methyl-aminopropylmethyldiethoxysilane, Nn-butyl-aminopropylmethyldimethoxysilane, Nn-butyl-aminopropylmethyldiethoxysilane Silane, N-Cyclohexylaminopropylmethyldimethoxysilane, N-cyclohexylaminopropylmethyldiethoxysilane, N-phenyl-aminopropylmethyldimethoxysilane, N-phenyl-aminopropylmethyldiethoxysilane, 3-[N- (2- (2-) Aminoethyl) amino] propylmethyldimethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldiethoxysilane, [3- [2- (2-aminoethylamino) ethylamino] propyl] methyldimethoxysilane , [3- [2- (2-Aminoethylamino) ethylamino] propyl] methyldiethoxysilane, N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (Triethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (trimethoxysilyl) propyl] hexamethylene Diamine and N, N'-bis- [3- (triethoxysilyl) propyl] hexamethylenedi Amine and the like can be mentioned. Examples of the aminoalkoxysilane include 3-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, and 3- [N- (2-aminoethyl) amino] propyltriethoxysilane. Preferably, 3- [N- (2-aminoethyl) amino] propyltriethoxysilane is more preferred.

(Alkoxysilane oligomer)
Further, examples of the aminosilane compound (D) include an alkoxysilane oligomer which is a hydrolysis condensate of an alkoxysilane containing aminoalkoxysilane. That is, the curable composition preferably contains, as the aminosilane compound (D), an alkoxysilane oligomer obtained by hydrolyzing an alkoxysilane containing an aminoalkoxysilane and then condensing it. Since the aminoalkoxysilane in the alkoxysilane oligomer is the same as the aminoalkoxysilane described above, detailed description thereof will be omitted here. The aminoalkoxysilane in the alkoxysilane oligomer may be used alone or in combination of two or more.

As the aminoalkoxysilane in the alkoxysilane oligomer, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane and 3- [N- (2-aminoethyl) amino] propyltriethoxysilane are preferable, and 3- [N- (2-aminoethyl) amino] propyltriethoxysilane is preferable. [N- (2-aminoethyl) amino] propyltriethoxysilane is more preferable.

In the alkoxysilane oligomer, the alkoxysilane preferably further contains an alkylalkoxysilane in addition to the aminoalkoxysilane. That is, as the aminosilane compound (D), an alkoxysilane oligomer which is a hydrolysis condensate of an alkoxysilane containing an aminoalkoxysilane and an alkylalkoxysilane is preferably mentioned. The curable composition preferably contains, as the aminosilane compound (D), an alkoxysilane oligomer obtained by hydrolyzing and then condensing an alkoxysilane containing an aminoalkoxysilane and an alkylalkoxysilane.

The alkylalkoxysilane means a compound in which at least one alkyl group and at least two alkoxy groups are directly bonded to a silicon atom. As the alkylalkoxysilane, one alkyl group and three alkoxy groups are directly bonded to a silicon atom, and a monoalkyltrialkoxysilane, and two alkyl groups and two alkoxy groups are silicon. Examples thereof include dialkyldialkoxysilanes that are directly bonded to an atom. Specific examples of the monoalkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and hexyltrimethoxysilane. Specific examples of the dialkyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane. Of these, monoalkyltrialkoxysilane is preferable, and ethyltriethoxysilane is more preferable. The alkylalkoxysilane may be used alone or in combination of two or more.

As the alkoxysilane oligomer, alkoxysilane oligomer (d1), which is a hydrolyzed condensate of aminoalkoxysilane, is preferably mentioned. That is, an alkoxysilane oligomer (d1) obtained by hydrolyzing and then condensing an alkoxysilane containing only aminoalkoxysilane is preferable. As the alkoxysilane oligomer (d1), a hydrolyzed condensate of 3- [N- (2-aminoethyl) amino] propyltrialkoxysilane and a hydrolyzed condensate of 3-aminopropyltrialkoxysilane are preferable. A hydrolyzed condensate of [N- (2-aminoethyl) amino] propyltrialkoxysilane is more preferred.

Further, as the alkoxysilane oligomer, an alkoxysilane oligomer (d2), which is a hydrolysis condensate of an alkylalkoxysilane and an aminoalkoxysilane, is preferably mentioned.

The alkoxysilane oligomer (d2) is preferably a hydrolyzed condensate of a monoalkyltrialkoxysilane and an aminoalkoxysilane in which one aminopropyl functional group and three alkoxy groups are directly bonded to a silicon atom. That is, as the alkoxysilane oligomer (d2), an alkoxysilane containing a monoalkyltrialkoxysilane and an aminoalkoxysilane in which one aminopropyl functional group and three alkoxy groups are directly bonded to a silicon atom is added. Preferred examples include an alkoxysilane oligomer obtained by decomposing and then condensing. Of these, a hydrolyzed condensate of monoalkyltrialkoxysilane and 3- [N- (2-aminoethyl) amino] propyltrialkoxysilane is more preferred, with ethyltriethoxysilane and 3- [N- (2). -Aminoethyl) Amino] Hydrolyzed condensates with propyltriethoxysilane are more preferred.

As the alkoxysilane oligomer (d2), a hydrolysis condensate of dialkyldialkoxysilane and aminoalkoxysilane in which one aminopropyl functional group and three alkoxy groups are directly bonded to a silicon atom is preferable. That is, as the alkoxysilane oligomer (d2), an alkoxysilane containing a dialkyldialkoxysilane and an aminoalkoxysilane in which one aminopropyl functional group and three alkoxy groups are directly bonded to a silicon atom is hydrolyzed. Preferred examples thereof include an alkoxysilane oligomer obtained by condensing the mixture.

The alkoxysilane oligomer preferably has an aminopropyl functional group. Since the aminopropyl functional group contained in the alkoxysilane oligomer is the same as the aminopropyl functional group possessed by the aminoalkoxysilane described above, detailed description thereof will be omitted here.

As the alkoxysilane oligomer, a commercially available product can be used. For example, the product name "Dynasilane 1146" manufactured by Evonik Dexa Co., Ltd. and "VX225" manufactured by Momentive Co., Ltd. may be mentioned.

In the alkoxysilane oligomer, the content of nitrogen atoms is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. When the content of nitrogen atoms is 1% by mass or more, it is possible to provide a curable composition having excellent adhesiveness and excellent extensibility after curing. The upper limit of the nitrogen atom content is not particularly limited, but is preferably 20% by mass or less, and more preferably 10% by mass or less. When the content of nitrogen atoms is 20% by mass or less, excellent rubber elasticity can be maintained even when the cured product of the curable composition becomes high temperature.

The content of nitrogen atoms in the alcoholicylan oligomer refers to a value measured based on CHN elemental analysis. For example, it can be obtained under the following measurement conditions.
-Device: CHN elemental analyzer (Vario EL III manufactured by Elementar)
-Sample amount: 10 mg
-Combustion tube temperature: 950 ° C
・ Reduction tube temperature: 500 ℃
・ Carrier gas: 200 mL / min
-Detector: TCD
-Standard sample: Acetanilide (standard sample for elemental analysis) C = 71.09%, H = 6.710%, N = 10.36%)
・ Quantitative method: Multi-inspection amount line method using standard sample

The aminosilane compound (D) preferably contains at least one of the aminoalkoxysilane and the alkoxysilane oligomer, but more preferably contains the alkoxysilane oligomer, and contains both the aminoalkoxysilane and the alkoxysilane oligomer. Is more preferable.

The aminosilane compound (D) is preferably liquid under the conditions of 25 ° C. and 0.10 MPa. By using the liquid aminosilane compound (D), the curable composition can exhibit good adhesiveness.

The viscosity of the aminosilane compound (D) at 20 ° C. is preferably 1 to 200 mPa · s, preferably 5 to 100 mPa · s. The viscosity of the aminosilane compound (D) at 20 ° C. refers to a value measured in accordance with JIS Z8803.

The content of the aminosilane compound (D) in the curable composition is preferably 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. 5 parts by mass is more preferable, and 1 to 3 parts by mass is particularly preferable. When the content of the aminosilane compound (D) is 0.1 parts by mass or more, the adhesiveness of the curable composition is improved. When the content of the aminosilane compound (D) is 10 parts by mass or less, the curability of the curable composition is improved.

[Silanol condensation catalyst (E)]
The curable composition contains a silanol condensation catalyst (E). The silanol condensation catalyst (E) is a silanol group formed by hydrolyzing a hydrolyzable silyl group contained in the polyalkylene oxide (A) and an alkoxysilyl group contained in the aminosilane compound (D). It is a catalyst for accelerating the dehydration condensation reaction of.

The silanol condensation catalyst (E) is not particularly limited, and for example, dioctyl tin monodecanete, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyl. Tin diacetate, dibutyltin phthalate, bis (dibutyltin lauric acid) oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (monoestermalate), tin octylate, dibutyltin octate, dioctyltin oxide, dibutyltin Organic tin compounds such as bis (triethoxysilicate), bis (dibutyltin bistriethoxysilicate) oxide, and dibutyltin oxybisethoxysilicate; organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. However, organic tin compounds are preferable, and dioctyl tin oxide is more preferable. These silanol condensation catalysts may be used alone or in combination of two or more.

The content of the silanol condensation catalyst (E) in the curable composition is preferably 1 to 10 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. Is more preferable. When the content of the silanol condensation catalyst (E) in the curable composition is 1 part by mass or more, the curing rate of the curable composition is increased and the time required for curing the curable composition is shortened. be able to. Further, when the content of the silanol condensation catalyst (E) in the curable composition is 10 parts by mass or less, the curable composition has an appropriate curing rate, and the storage stability and handleability of the curable composition Can be improved.

[Plasticizer]
The curable composition preferably contains a plasticizer. As the plasticizer, in the case of other than polymers and oligomers, compounds having a molecular weight of 300 to 10,000 are used. In the case of polymers and oligomers, as the plasticizer, polymers or oligomers having a number average molecular weight of 400 to 11,000 are used. Specific examples thereof include phthalates such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate, polyalkylene oxides such as polypropylene glycol, and acrylic polymers, and acrylic polymers are preferable.

The acrylic polymer used as a plasticizer preferably does not contain a hydrolyzable silyl group. The weight average molecular weight of the acrylic polymer used as the plasticizer is preferably 500 to 10,000, more preferably 1,000 to 5,000. When the weight average molecular weight of the acrylic polymer is 500 or more, the bleed-out of the acrylic polymer can be suppressed. Further, the weight average molecular weight of the acrylic polymer is 10,000 or less. By fully plasticizing the curable composition, the cured product of the curable composition has excellent rubber elasticity.

The weight average molecular weight of the acrylic polymer used as the plasticizer is a value measured by polystyrene conversion by the GPC (gel permeation chromatography) method. The specific measurement method and measurement conditions are the same as the above-mentioned measurement procedure for polyalkylene oxide.

The acrylic polymer used as a plasticizer is preferably a polymer obtained by addition polymerization of an acrylic monomer having an ethylenically unsaturated double bond in the above ethylenically unsaturated double bond. be.

The content of the plasticizer in the curable composition is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and 1 to 100 parts by mass with respect to 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. 85 parts by mass is particularly preferable. When the content of the plasticizer in the curable composition is 100 parts by mass or less, bleed-out of the plasticizer can be suppressed and contamination of the cured product of the curable composition can be suppressed.

[filler]
The curable composition preferably further contains a filler. According to the filler, it is possible to provide a curable composition capable of obtaining a cured product having excellent mechanical strength.

Examples of the filler include calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, silicic anhydride, fine powder silica, calcium silicate, titanium dioxide, clay, talc, carbon black, and glass balloons. Calcium carbonate is preferable, and colloidal calcium carbonate and heavy calcium carbonate are preferable. These fillers may be used alone or in combination of two or more.

The average particle size of calcium carbonate is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. According to calcium carbonate having such an average particle size, a cured product having excellent mechanical strength and extensibility can be obtained, and a curable composition having excellent adhesiveness can be obtained. Can be provided.

Further, calcium carbonate is preferably surface-treated with a fatty acid, a fatty acid ester, or the like. According to the calcium carbonate surface-treated with a fatty acid or a fatty acid ester, thixotropy can be imparted to the curable composition and the aggregation of calcium carbonate can be suppressed.

The content of the filler in the curable composition is preferably 1 to 700 parts by mass, more preferably 10 to 250 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. ~ 200 parts by mass is particularly preferable. When the content of the filler in the curable composition is 1 part by mass or more, the effect of adding the filler can be sufficiently obtained. Further, when the content of the filler in the curable composition is 700 parts by mass or less, the cured product obtained by curing the curable composition has excellent rubber elasticity.

[Dehydrating agent]
The curable composition preferably further contains a dehydrating agent. According to the dehydrating agent, when the curable composition is stored, it is possible to prevent the curable composition from being cured by the moisture contained in the air or the like.

Dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthostate. , Ethyl compounds such as ethyl orthostate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferable.

The content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. .. When the content of the dehydrating agent in the curable composition is 0.5 parts by mass or more, the effect obtained by the dehydrating agent can be sufficiently obtained. Further, when the content of the dehydrating agent in the curable composition is 20 parts by mass or less, the curable composition has excellent curability.

[Light stabilizer]
The curable composition preferably further contains a light stabilizer, more preferably a hindered amine-based light stabilizer. According to the hindered amine-based light stabilizer, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing.

Examples of the hindered amine-based light stabilizer include a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate. , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4) Polycondensate of −piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-) Tetramethylbutyl) amino-1,3,5-triazin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6) −Tetramethyl-4-piperidyl) imino}], polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol.

The content of the hindered amine-based light stabilizer in the curable composition is preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. Parts by mass are more preferred.

[Other additives]
The curable composition may contain other additives such as thixotropic agents, antioxidants, UV absorbers, pigments, dyes, antioxidants, and solvents. Among them, thixotropic agents, ultraviolet absorbers, and antioxidants are preferably mentioned.

(Thixotropic agent)
The thixotropy-imparting agent may be any as long as it can exhibit thixotropy in the curable composition. Preferred examples of the thixotropy-imparting agent include hydrogenated castor oil, fatty acid bisamide, and fumed silica.

The content of the thixotropy-imparting agent in the curable composition is preferably 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass with respect to 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. Is more preferable. When the content of the thixotropy-imparting agent is 0.1 parts by mass or more, thixotropy can be effectively imparted to the curable composition. Further, when the content of the thixotropy-imparting agent is 200 parts by mass or less, the curable composition has an appropriate viscosity, and the handleability of the curable composition is improved.

(UV absorber)
Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and the like, and a benzotriazole-based ultraviolet absorber is preferable. The content of the ultraviolet absorber in the curable composition is preferably 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. The portion is more preferable.

(Antioxidant)
Examples of the antioxidant include a hindered phenolic antioxidant, a monophenolic antioxidant, a bisphenolic antioxidant, a polyphenolic antioxidant and the like, and the hindered phenolic antioxidant is preferable. Be done. The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide (A) having a hydrolyzable silyl group. More preferred.

Since the curable composition has excellent adhesiveness and can form a cured product capable of maintaining excellent rubber elasticity for a long period of time, it is possible to form a sealant, a coating material, an adhesive, and a paint. It can be used for various purposes. Of these, it is preferably used as a sealing material, and more preferably used as a joint structure sealing material.

As a method of applying the curable composition to the joint portion to obtain a joint structure, a method of filling the joint portion with the curable composition and then curing and curing the curable composition is used. The obtained joint structure has a wall member constituting the wall portion of the building structure and a cured product of the curable composition filled in the joint portion formed between the wall members adjacent to each other. There is. Examples of the wall portion of the building structure include an outer wall, an inner wall, and a ceiling portion. Examples of the wall member include an outer wall member, an inner wall member, and a ceiling member.

The material constituting the wall member is not particularly limited. Examples of the wall member include a mortar plate, a concrete plate, a ceramic siding board, a metal siding board, an ALC plate, a ceramic plate, and a metal plate. With the conventional curable composition, it was difficult to adhere to a wall member such as a cement plate such as a ceramic plate or a lightweight cement plate. However, even with such a poorly adhesive wall member, the curable composition of the present invention can be used. It can exhibit excellent adhesiveness. Therefore, since the effect of the present invention can be particularly exhibited, a poorly adhesive wall member such as a ceramic plate or a cement plate is preferably used as the wall member. The porcelain plate is preferably a plate made of porcelain. Ceramics is a general term for sintered products that utilize the sinterability of mineral powder. Examples of pottery include porcelain and pottery. Porcelain is a type of porcelain that has been baked well to the extent that the dough does not absorb water at all. In addition, pottery is a type of pottery in which the dough is glazed to a certain degree of water absorption.

The joint portion is not particularly limited, and examples thereof include joint portions on the outer wall, inner wall, and ceiling of the building structure. Since the curable composition of the present invention can maintain excellent rubber elasticity for a long period of time after curing, it is caused by expansion and contraction of members due to temperature changes such as air temperature and sunshine, or by actions such as vibration and wind pressure. It exhibits excellent followability to changes in the width of the joint due to the above, and can prevent damage to members and water leakage into the building structure. Therefore, it is suitably used for sealing a joint portion having a large change in width, which is also called a so-called "working joint", such as a joint portion on an outer wall of a building structure.

Since the curable composition of the present invention has the above-mentioned structure, it can exhibit excellent adhesiveness and can maintain excellent rubber elasticity for a long period of time after curing.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

The following raw materials were used in the production of the curable compositions of Examples and Comparative Examples.
[Organic polymer (I)]
(Polyalkylene oxide (A))
Polyalkylene oxide (A1) (polyalkylene oxide containing a methyldimethoxysilyl group and having a polypropylene oxide main chain skeleton, product name "Exester ES-S4530" manufactured by AGC Inc., number average molecular weight (Mn): 25, 000, molecular weight distribution (Mw / Mn): 1.15)
Polyalkylene oxide (A2) (polyalkylene oxide containing a methyldimethoxysilyl group and having a polypropylene oxide main chain skeleton, product name "SX6735D" manufactured by AGC Inc., number average molecular weight (Mn): 30,000, molecular weight distribution (Mw / Mn): 1.15)
Polyalkylene oxide (A3) (polyalkylene oxide containing a methyldimethoxysilyl group and having a polypropylene oxide main chain skeleton, product name "Cyril SAX720" manufactured by Kaneka Corporation, number average molecular weight (Mn): 25,000, molecular weight distribution (Mw / Mn): 1.42 "
Polyalkylene oxide (A4) containing no hydrolyzable silyl group (Product name "Exester ES-T2420" manufactured by AGC Inc., number average molecular weight (Mn): 17,000, molecular weight distribution (Mw / Mn): 1.4)

(Acrylic polymer (B))
The main chain skeleton is composed of a copolymer of methyl methacrylate and n-butyl acrylate (content of methyl methacrylate component: 25% by weight, content of n-butyl acrylate component: 75% by weight), and a side chain of the main chain skeleton. Alternatively, an acrylic polymer (B1) having a trimethoxysilyl group at the end, product name "Alfon US-6150" manufactured by Toa Synthetic Co., Ltd., weight average molecular weight: 3,200).

[Amine compound (C)]
Amine compound (C1) (behenyl propylene diamine melting point 60 ° C, product name "Nissan Amine DV" manufactured by NOF CORPORATION)
Amine compound (C2) (stearylamine melting point 50 ° C)

[Aminosilane compound (D)]
Aminosilane compound (D1) (alkoxysilane oligomer, which is a hydrolysis condensate of ethyltriethoxysilane and 3- [N- (2-aminoethyl) amino] propyltriethoxysilane, content of nitrogen atom: 6% by mass, Liquid under the conditions of 25 ° C. and 0.10 MPa, viscosity (20 ° C.): 20 mPa · s, product name "Dynasilane 1146" manufactured by Evonik Degusa Japan Co., Ltd.)
Aminosilane compound (D2) (3-aminopropyltriethoxysilane, liquid under the conditions of 25 ° C. and 0.10 MPa, viscosity (20 ° C.): 4 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd. Product name "KBE-903" )

[Silanol condensation catalyst (E)]
Silanol condensation catalyst (E1) (dioctyl tin oxide)

[Plasticizer]
Plasticizer (1) (Acrylic polymer containing no hydrolyzable silyl group, weight average molecular weight: 2,000, manufactured by Toagosei Co., Ltd. Product name "UP1110")

[filler]
Colloidal calcium carbonate (Product name "PLS-505" manufactured by Konoshima Chemical Co., Ltd., average particle size: 0.1 μm)
Heavy calcium carbonate (Product name "Whiten SB" manufactured by Shiraishi Calcium Co., Ltd., average particle size: 2.0 μm)

[Dehydrating agent]
Vinyl trimetoshisilane (Product name "KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.)
[UV absorber]
Benzotriazole UV absorber (BASF Japan product name "Tinubin 326")
[Antioxidant]
Hindered phenolic antioxidant (BASF Japan product name "Irganox 1010")

(Examples 1 to 6 and Comparative Examples 1 to 2)
The above-mentioned polyalkylene oxide (A1), polyalkylene oxide (A2), polyalkylene oxide (A3), polyalkylene oxide (A4), acrylic polymer (B1), amine compound (C1), amine compound (C2). , Aminosilane compound (D1), Aminosilane compound (D2), Silanol condensation catalyst (E1), Plasticizer (1), Colloidal calcium carbonate, Heavy calcium carbonate, Vinyl trimethosisilane, Bentriazole-based ultraviolet absorber, and Hinderd A curable composition was obtained by mixing the phenolic antioxidants in a sealed stirrer so as to have the blending amounts shown in Table 1 while reducing the pressure until uniform.

[evaluation]
(Elongation at maximum load: Initial)
Using the curable composition, an H-type test piece was prepared in accordance with JIS A1439 4.21. Specifically, two ceramic plates (thickness 20 mm, length 50 mm x width 50 mm, product name "Super Tri-Wall" manufactured by Tsuruya Co., Ltd.) are used, and a spacer is sandwiched between these ceramic plates to form a rectangular parallelepiped in the center between the ceramic plates. A shaped space (length 12 mm × width 50 mm × height 12 mm) was formed. This space was filled with a curable composition to prevent air from entering. After filling the curable composition, the curable composition was left to stand for 14 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. After that, the curable composition was left to stand for 14 days in an atmosphere at a temperature of 30 ° C. By curing and curing the curable composition, an H-type test piece was prepared in which two ceramic plates were adhered and integrated by the cured product of the curable composition.

Then, the H-type test piece immediately after production was subjected to a tensile test at a tensile speed of 50 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50% in accordance with JIS A1439, and the elongation [%] under a maximum load was measured. bottom. Further, after the tensile test was completed, the fractured form of the cured product of the curable composition was visually confirmed and evaluated according to the following criteria. The results obtained are listed in the "Initial" column of Table 1.

(Elongation at maximum load: after durability)
Further, as a durability evaluation, an H-type test piece was prepared in the same manner as described above. Immediately after preparation, the H-type test piece was exposed to an atmosphere of 80 ° C. for 1 month, and then left to stand in an atmosphere of 23 ° C. and a relative humidity of 50% for another 24 hours. %] Was measured. Further, after the tensile test, the fractured form of the cured product of the curable composition was visually confirmed and evaluated according to the following criteria. The obtained results are listed in the "After endurance" column in Table 1.

The criteria for evaluating the fractured form of the cured product of the curable composition is that after the tensile test is completed, the cured product of the curable composition is coagulated and fractured as "CF", and the cured product of the curable composition is interfacially fractured. Was set to "AF".

The cohesive failure of the cured product means a state in which the cured product itself is broken in the tensile test. Further, the interfacial fracture of the cured product means a state of peeling at the interface between the porcelain plate and the cured product in the tensile test. The higher the adhesive strength of the cured product of the curable composition, the more cohesive fracture occurs, and the lower the adhesive strength of the cured product of the curable composition, the more interfacial fracture occurs.

The curable composition of the present invention has excellent adhesiveness and can maintain excellent rubber elasticity for a long period of time after curing. Therefore, for example, an outer wall member constituting an outer wall of a building structure. It can be suitably used as a filler for the joint formed between the two.

Claims (8)

Curability characterized by containing an organic polymer (I) having a hydrolyzable silyl group, an amine compound (C) having a melting point of 55 ° C. or higher, an aminosilane compound (D), and a silanol condensation catalyst (E). Composition. The curable composition according to claim 1, wherein the organic polymer (I) having a hydrolyzable silyl group contains a polyalkylene oxide (A) having a hydrolyzable silyl group. The polyalkylene oxide (A) having a hydrolyzable silyl group is characterized by having a number average molecular weight (Mn) of 20,000 to 50,000 and a molecular weight distribution (Mw / Mn) of 1.3 or less. The curable composition according to claim 2. The invention according to any one of claims 1 to 3, wherein the organic polymer (I) having a hydrolyzable silyl group contains an acrylic polymer (B) having a hydrolyzable silyl group. Curable composition. The curable composition according to any one of claims 1 to 4, wherein the amine compound (C) contains a diamine compound having a melting point of 55 ° C. or higher. The curable composition according to any one of claims 1 to 5, wherein the aminosilane compound (D) contains a hydrolyzed condensate of alkoxysilane containing aminoalkoxysilane. The curable composition according to any one of claims 1 to 6, wherein the aminosilane compound (D) is a hydrolyzed condensate of an alkylalkoxysilane and an aminoalkoxysilane. The wall members that make up the walls of the building structure and
The cured product of the curable composition according to any one of claims 1 to 7, which is filled in the joint portion formed between the wall members.
A joint structure characterized by containing.