JP2004169020A - Curable composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which can give a cured product exhibiting excellent weatherability, and a sealing material and an adhesive which use the curable composition. <P>SOLUTION: The curable composition comprises 100 pts.wt. organic polymer having at least one crosslinkable and hydrolyzable silyl group and 30-200 pts.wt. calcium carbonate having a BET specific surface area of 2-15 m<SP>2</SP>/g. The curable composition comprises 100 pts.wt. organic polymer having at least one crosslinkable and hydrolyzable silyl group and 30-200 pts.wt. and calcium carbonate having an average particle diameter of 0.3-2 μm. The above curable composition comprises 0.1-100 pts.wt. phyllosilicate, and further comprises 0.1-20 light stabilizer and/or 0.1-20 pts.wt. ultraviolet absorber. In the above curable composition, the principal chain of the organic polymer is composed essentially of a polyether polymer and/or a vinyl polymer. The sealing material and the adhesive comprise the above curing composition. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a curable composition that cures at room temperature by reacting with moisture in the air, and a sealing material and an adhesive using the curable composition.

As a curable composition which is based on an organic polymer containing a reactive silyl group as a base (main component) and is suitable as a sealing material having excellent weather resistance, for example, Patent Document 1 below discloses a reactive silyl group-containing oxy group. A curable composition containing an alkylene polymer, a benzotriazole-based UV absorber and a hindered phenol-based antioxidant as essential components is disclosed.

However, the cured product of the curable composition has a problem that the weather resistance is limited to about 2000 hours as measured by a sunshine weatherometer, and is not always sufficient. Specifically, the cured product subjected to the long-term weather resistance test causes a decrease in physical properties, cracks, whitening, and the like. Among them, cracks in the cured product are not only unfavorable in appearance, but also significantly reduce the elongation of the cured product, accelerate the deterioration of the cured product due to the intrusion of water from the cracks, etc., and the outer wall using this cured product There is a problem that it also has an adverse effect on the like.

As such a method for improving the weather resistance, for example, Patent Document 2 below discloses an organic polymer containing a crosslinkable hydrolyzable silyl group, and a polymer unit based on a fluoroolefin with respect to all polymer units. 20 to 70 mol%, a fluorine-containing polymer unit having a photocurable functional group in a proportion of 1 to 80 mol% based on all polymer units, and other polymer units in a ratio of 0 to 70 mol% based on all polymer units A curable composition containing a copolymer is disclosed.

However, the curable composition has a problem that the effect of improving the weather resistance is insufficient, and the curable composition is expensive because of using a fluorinated copolymer, and has poor practicality.
JP-A-5-287186 JP-A-9-208782

In view of the above problems, an object of the present invention is to provide a curable composition capable of obtaining a cured product exhibiting excellent weather resistance, and a sealing material and an adhesive using the curable composition. It is in.

The curable composition according to the invention of claim 1 (hereinafter referred to as “the present invention 1”) has a BET ratio of 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. It is characterized in that 30 to ²⁰⁰ parts by weight of calcium carbonate having a surface area of ² to 15 m ² / g is blended.

The curable composition according to the invention according to claim 2 (hereinafter referred to as “the present invention 2”) has an average particle size of 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. It is characterized in that 30 to 200 parts by weight of calcium carbonate having a diameter of 0.3 to 2 μm is blended.

The curable composition according to the third aspect of the present invention is characterized in that the curable composition according to the first or second aspect further comprises 0.1 to 100 parts by weight of a layered silicate. Features.

The curable composition according to the invention according to claim 4 is the curable composition according to any one of claims 1 to 3, further comprising 0.1 to 20 parts by weight of a light stabilizer and / or Alternatively, 0.1 to 20 parts by weight of an ultraviolet absorber is blended.

According to a fifth aspect of the present invention, there is provided the curable composition according to any one of the first to fourth aspects, wherein the main chain of the organic polymer is essentially a polyether type. It is characterized by comprising a polymer and / or a vinyl polymer.

A sealing material according to a sixth aspect of the present invention comprises the curable composition according to any one of the first to fifth aspects.

Further, an adhesive according to the invention of claim 7 is characterized by comprising the curable composition of any one of claims 1 to 5.

The curable composition of the present invention 1 has a BET specific surface area of ² to 15 m ² / g and a calcium carbonate of 30 to 200 parts by weight per 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. Parts by weight.

In addition, the curable composition of the present invention 2 has an average particle diameter of 0.3 to 2 μm based on 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. 200 parts by weight are blended.

The organic polymer used in the curable compositions of the present invention 1 and the present invention 2 contains at least one hydrolyzable silyl group which can be cross-linked by forming a siloxane bond. It is formed by a hydroxyl group or a hydrolyzable group bonded to.

The hydrolyzable group bonded to the silicon atom is not particularly limited, but includes, for example, hydrogen, a halogen atom, an alkoxyl group such as a methoxy group or an ethoxy group, an acyloxide group, a ketoximate group, an amino group, and an amide. Groups, acid amide groups, aminooxy groups, mercapto groups, alkenyl oxide groups and the like. These hydrolyzable groups may be used alone or in combination of two or more.

The crosslinkable hydrolyzable silyl group is not particularly limited because it does not generate harmful by-products after the reaction, but for example, an alkoxysilyl group such as a methoxysilyl group or an ethoxysilyl group is preferable. Used for These crosslinkable hydrolyzable silyl groups may be used alone or in combination of two or more.

The main chain of the organic polymer containing at least one hydrolyzable silyl group which can be crosslinked by forming the siloxane bond is not particularly limited, and examples thereof include a polyether polymer and a vinyl polymer. Examples thereof include a polymer, a polyester polymer, a polycarbonate polymer, and a polyolefin polymer. Among them, a polyether polymer and / or a vinyl polymer are preferably used. That is, the main chain of the organic polymer used in the present invention is preferably essentially composed of a polyether-based polymer or a vinyl-based polymer, and both the polyether-based polymer portion and the vinyl-based polymer portion are preferably used. May be provided. Further, an organic polymer whose main chain consists essentially of only a polyether polymer and an organic polymer whose main chain consists essentially of only a vinyl polymer may be used in an appropriate mixture.

Hereinafter, the organic polymer (a) whose main chain consists essentially of a polyether polymer and the organic polymer (b) whose main chain consists essentially of a vinyl polymer will be described.

[Organic polymer (a) whose main chain consists essentially of a polyether polymer]
The main chain structure of the organic polymer (a) whose main chain consists essentially of a polyether polymer and contains at least one crosslinkable hydrolyzable silyl group is not particularly limited, For example, polyoxyethylene polymer, polyoxypropylene polymer, polyoxybutylene polymer and the like, among which, when the cured product of the curable composition is excellent in water resistance, and when used as a sealing material or an adhesive Since a higher rubber elasticity can be ensured, a polyoxypropylene polymer is preferably used.

The organic polymer (a) is not particularly limited, since the balance between the workability of the curable composition and the elongation of the cured product is excellent, but the number average molecular weight is 10,000 to 3 It is preferable that the molecular weight distribution Mw / Mn (weight average molecular weight / number average molecular weight) is 1.6 or less.

When the number average molecular weight of the organic polymer (a) is less than 10,000, the elongation of the cured product of the curable composition becomes insufficient, and when used as a sealing material, for example, the followability to the ground surface is reduced. If the number average molecular weight of the organic polymer (a) exceeds 30,000, the viscosity of the curable composition before curing becomes too high, and various compounding agents (additives) may be added. In some cases, the workability of the compounding step of preparing the sealing material and the adhesive may be reduced.

The organic polymer (a) whose main chain consists essentially of a polyether-based polymer is generally called a modified silicone polymer, and specific examples thereof are not particularly limited. "MS Polymer S-203" and "MS Polymer S-303" manufactured by Kaneka Corporation, and "Silyl SAT-200", "Silyl SAT-350", and "Silyl SAT-400" also manufactured by Kanegafuchi Chemical Industry Co., Ltd. And Exeter ESS-2410, Exeter ESS-2420, Exester ESS-3430 and Exester ESS-3620 manufactured by Asahi Glass Co., Ltd. These organic polymers (a) may be used alone or in combination of two or more.

Further, specific examples of the organic polymer whose main chain is essentially composed of a polyether-based polymer and a vinyl-based polymer described below are not particularly limited. The name “MS polymer MA-903” and the like can be mentioned.

[Organic polymer (b) whose main chain consists essentially of a vinyl polymer]
The organic polymer (b) whose main chain consists essentially of a vinyl polymer and contains at least one crosslinkable hydrolyzable silyl group contains, for example, a vinyl monomer and the above hydrolyzable silyl group. It is obtained by copolymerization with a monomer, and may contain a unit composed of a urethane bond or a siloxane bond in a range of 50% by weight or less as a part of a main chain or a side chain.

The organic polymer (b) is not particularly limited, but is produced, for example, by the following method.
(1) A method of reacting a (meth) acrylate copolymer having an allyl group with a hydrosilicon compound in the presence of a Group VIII transition metal, as described in JP-A-54-36395.
(2) As described in JP-A-57-179210, a vinyl monomer is copolymerized in the presence of an alkyl (meth) acrylate containing an alkoxysilyl group and a chain transfer agent containing a mercapto group. Method.
(3) A method of copolymerizing a vinyl monomer in the presence of a bifunctional radically polymerizable compound and a mercaptan containing an alkoxysilyl group as a chain transfer agent as described in JP-A-59-78222. .
(4) A method in which a vinyl monomer is used as a polymerization initiator to polymerize using an azobisnitrile compound containing an alkoxysilyl group as described in JP-A-60-23405.
(5) A method for producing a vinyl polymer by a living radical polymerization method, as described in JP-A-11-130931.

The vinyl-based monomer used in the production of the organic polymer (b) is not particularly limited, but, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) ) Acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate Rate, tetrahydrofurfuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Epoxy acrylate, polyester acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl ( (Meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxy (Meth) acrylates such as ethyl phthalate, 2-[(meth) acryloyloxy] ethyl 2-hydroxypropyl phthalate, methyldimethoxypropyl (meth) acrylate; styrene, indene, α-methyl Styrene derivatives such as tylene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene; vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl caproate , Vinyl benzoate, compounds having a vinyl ester group such as vinyl cinnamate; 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 (4-vinyloxy) butyl, 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, di (4-vinyloxy) butyl isophthalate, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyl succinate trimethylolpropane trivinyl ether 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol-monovinyl ether, Compounds having a vinyloxy group, such as tylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether; maleic anhydride, N-vinylpyrrolidone, and N-vinylmorpholine , (Meth) acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide and the like. Incidentally, for example, (meth) acrylate referred to in the present invention means acrylate or methacrylate.

Specific examples of the vinyl monomer include, but are not particularly limited to, for example, “Aronix M-5700” (trade name) which is a vinyl monomer manufactured by Toa Gosei Chemical Industry Co., Ltd. Trade name "AS-6", "AN-6", "AA-6", "AB-6", "AK-5", which is a vinyl macromonomer, a product which is a vinyl monomer manufactured by Daicel Chemical Industries, Ltd. Names include "Placcel FA-1", "Placcel FM-1", and "Placcel FM-4". These vinyl monomers (including vinyl macromonomers) may be used alone or in combination of two or more.

Among the organic polymers (b) having a main chain consisting essentially of a vinyl polymer and containing at least one crosslinkable hydrolyzable silyl group, acrylic acid and carbon atoms of an alkyl group are excellent in flexibility. An organic polymer (b) having a main chain of a (meth) acrylate copolymer composed of an alkyl (meth) acrylate having 1 to 12 alkyl groups is preferable, and more preferably acrylic acid and an alkyl group having 2 to 2 carbon atoms. An organic polymer (b) having a main chain of a (meth) acrylate-based copolymer comprising an alkyl (meth) acrylate of No. 8

The crosslinkable hydrolyzable silyl group is not particularly limited because it does not generate harmful by-products after the reaction, and examples thereof include an alkoxysilyl group such as a methoxysilyl group and an ethoxysilyl group. It is preferably used. These crosslinkable hydrolyzable silyl groups may be used alone or in combination of two or more.

The organic polymer (b) is not particularly limited since the balance between the workability of the curable composition and the elongation of the cured product is excellent, but the number average molecular weight is 5,000 to 200,000. , More preferably 10,000 to 60,000, and a molecular weight distribution (Mw / Mn) of 1.6 or less.

When the number average molecular weight of the organic polymer (b) is less than 5,000, the elongation of the cured product of the curable composition becomes insufficient, and when used as a sealing material, for example, the followability to the joint surface is reduced. When the number average molecular weight of the organic polymer (b) exceeds 200,000, the viscosity of the curable composition before curing becomes too high, and various compounding agents (additives) may be added. The workability of the compounding process for preparing the sealing material and the adhesive may be reduced.

In the curable composition of the present invention, the organic polymer (a) and the organic polymer (b) may be used alone or in combination. By using the organic polymer (a) and the organic polymer (b) together, it is possible to increase the water resistance of the cured product of the curable composition, and to enhance the rubber elasticity when used as a sealing material or an adhesive. .

When the organic polymer (a) and the organic polymer (b) are used in combination, the mixing ratio is 0.1 to 200 parts by weight of the organic polymer (a) with respect to 100 parts by weight of the organic polymer (b). And more preferably 0.5 to 100 parts by weight of the organic polymer (a).

If the blending ratio of the organic polymer (a) is less than 0.1 part by weight with respect to 100 parts by weight of the organic polymer (b), a sufficient adhesiveness improving effect may not be obtained, and conversely, the organic polymer ( b) When the blending ratio of the organic polymer (a) to 100 parts by weight exceeds 200 parts by weight, the weatherability of the cured product of the curable composition may be insufficient, and the effect of improving the adhesiveness is not so large. Because it does not become high.

The curable composition of the present invention 1 is obtained by blending 30 to 200 parts by weight of calcium carbonate having a BET specific surface area of ² to 15 m ² / g with respect to 100 parts by weight of the above-mentioned organic polymer.

The curable composition of the present invention 2 is obtained by blending 30 to 200 parts by weight of calcium carbonate having an average particle diameter of 0.3 to 2 μm with respect to 100 parts by weight of the above-mentioned organic polymer.

The most preferred calcium carbonate used in the curable composition of the present invention is a calcium carbonate having a BET specific surface area of ² to 15 m ² / g and an average particle diameter of 0.3 to 2 μm.

By blending calcium carbonate having the specific BET specific surface area and / or average particle diameter with respect to the organic polymer, when a weather resistance test is performed, the cured product of the curable composition has a surface crack. It is effectively suppressed and exhibits excellent weather resistance.

The calcium carbonate used in the curable composition of the present invention may be any calcium carbonate as long as the BET specific surface area is ² to 15 m ² / g and / or the average particle diameter is 0.1 to 2.0 μm, Although not particularly limited, for example, colloidal calcium carbonate, light calcium carbonate such as precipitated calcium carbonate, limestone, chalk, heavy calcium carbonate composed of stone powder, etc., and these are surface-treated with an organic acid such as a fatty acid Surface-treated calcium carbonate and the like. Among them, light calcium carbonate and surface-treated light calcium carbonate are preferably used because the particle diameter is uniform. These calcium carbonates may be used alone or in combination of two or more.

The calcium carbonate used in the curable composition of the present invention 1 needs to have a BET specific surface area of ² to 15 m ² / g, preferably 5 to 14 m ² / g. When the calcium carbonate has a BET specific surface area of less than 2 m ² / g, dispersibility (kneading properties) with respect to the organic polymer is reduced, or the cured product of the curable composition has insufficient surface smoothness. If the calcium carbonate has a BET specific surface area of more than 15 m ² / g, the occurrence of surface cracks in the cured product of the curable composition cannot be sufficiently suppressed.

The BET specific surface area of the above calcium carbonate means a BET specific surface area measured by the following method.
[Measurement method of BET specific surface area] A fixed amount of calcium carbonate is weighed as a measurement sample, placed in a sample cell, dried in a vacuum dryer at 110 ° C for 60 minutes, and allowed to cool in a desiccator. Next, the sample cell was attached to the apparatus, degassing was performed by heating at 110 ° C. for 10 minutes with a mantle heater, then the mantle heater was removed, and a dewar bottle containing ice water was applied thereto to correct dead space at 0 ° C. Set pressure. Next, the Dewar bottle containing the ice water is removed, water droplets adhering to the sample cell are wiped off, and quickly set in a liquid nitrogen Dewar bottle. Measure the surface area. In this case, the nitrogen gas introduction pressure is set to 29.4 to 39.2 kPa.

The calcium carbonate used in the curable composition of the present invention 2 needs to have an average particle diameter of 0.3 to 2 μm, and preferably 0.5 to 1 μm. When the average particle size of the calcium carbonate is less than 0.3 μm, the surface area of the calcium carbonate becomes too large, and the generation of surface cracks of the cured product of the curable composition cannot be sufficiently suppressed. When the average particle size exceeds 2 μm, the dispersibility (kneading property) with respect to the organic polymer decreases, and the surface smoothness of the cured product of the curable composition becomes insufficient.

The average particle diameter of the calcium carbonate means an average particle diameter measured by the following method.
[Measurement method of average particle size] Using a scanning electron microscope SEM (for example, manufactured by JEOL Ltd.), 100 particles of calcium carbonate are observed, the particle size is measured, and the average particle size is calculated.

The present inventors, when performing a weather resistance test of a cured product of a curable composition containing calcium carbonate, cracks on the surface of the cured product are generated from the surface of the calcium carbonate, and the cause is the surface of the calcium carbonate. It was found that stress concentration occurred in In order to suppress the occurrence of cracks on the surface of the cured product, it has been found that it is effective to use a material having a relatively small surface area per unit volume of calcium carbonate, that is, a material having a relatively large particle size. Was. On the other hand, as the calcium carbonate used in the curable composition, it is general to use a calcium carbonate having as small a particle size as possible in order to secure the surface smoothness of the cured product of the curable composition.

In view of the above points, the present inventors have intensively studied the preferred particle size of calcium carbonate. As a result, the calcium carbonate having a BET specific surface area of ² to 15 m ² / g and / or an average particle size of 0.3 to ² μm was obtained. By using this, the occurrence of cracks on the surface of the cured product is drastically suppressed, and a curable composition exhibiting excellent weather resistance has been obtained.

The curable composition of the present invention needs to contain 30 to 200 parts by weight of the above calcium carbonate based on 100 parts by weight of the organic polymer, and preferably 80 to 150 parts by weight.

If the amount of the calcium carbonate is less than 30 parts by weight based on 100 parts by weight of the organic polymer, the occurrence of surface cracks on the cured product of the curable composition cannot be sufficiently suppressed. If the amount of the calcium carbonate is more than 200 parts by weight based on part by weight, the cured product of the curable composition becomes insufficient in flexibility and elongation.

The curable composition of the present invention preferably further contains 0.1 to 100 parts by weight of a layered silicate, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the organic polymer. And particularly preferably 1 to 10 parts by weight. By blending the layered silicate with the organic polymer, the cured product of the curable composition exhibits more excellent weather resistance and also has excellent flame retardancy.

When the compounding amount of the layered silicate with respect to 100 parts by weight of the organic polymer is less than 0.1 part by weight, the effect of improving the weather resistance of the cured product of the curable composition may not be sufficiently obtained, or flame retardancy may be imparted. Conversely, when the amount of the layered silicate with respect to 100 parts by weight of the organic polymer exceeds 100 parts by weight, the viscosity of the curable composition becomes too high, and workability and productivity may be reduced. is there.

The layered silicate compounded in the curable composition of the present invention means a silicate mineral having exchangeable cations between crystal layers.

The layered silicate is not particularly limited, but includes, for example, smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. Among them, montmorillonite and swellable mica are preferably used. These layered silicates may be natural products or synthetic products. These layered silicates may be used alone or in combination of two or more.

As the layered silicate, it is preferable to use a smectite-based clay mineral or swelling mica having a large shape anisotropy effect defined by the following relational expression (1). By using a layered silicate having a large shape anisotropy effect, the cured product of the curable composition of the present invention exhibits excellent mechanical strength and gas barrier properties.
Shape anisotropy effect = Area of crystal surface (A) / Area of crystal end face (B) (1)
FIG. 1 schematically shows the crystal surface (A) and the crystal end surface (B) of the layered silicate.

Although the shape of the layered silicate is not particularly limited, the average length of the crystal flakes obtained by crushing the aggregated structure is 0.01 to 3 μm, the thickness is 0.001 to 1 μm, and the aspect ratio is 20 to 500. The average length is preferably 0.05 to 2 μm, the thickness is 0.01 to 0.5 μm, and the aspect ratio is 50 to 200.

The exchangeable cations existing between the crystal layers of the layered silicate are ions of metals such as sodium and calcium present on the crystal surface of the layered silicate, and the ions of these metals are cationic. Since it has an ion exchange property with the substance, various substances having a cationic property can be inserted (intercalated) or trapped between the crystal layers of the layered silicate.

The cation exchange capacity of the layered silicate is not particularly limited, but is preferably 50 to 200 meq / 100 g. When the cation exchange capacity of the layered silicate is less than 50 milliequivalents / 100 g, the amount of the cationic substance inserted or trapped between the crystal layers of the layered silicate by ion exchange is reduced, so that the crystal layers can be sufficiently separated. When the cation exchange capacity of the layered silicate exceeds 200 meq / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may not be formed. May be difficult to peel off.

The layered silicate is preferably non-polarized (hydrophobicized) by previously performing ion exchange between the crystal layers with a cationic surfactant. By previously depolarizing (hydrophobicizing) the crystal layers of the layered silicate, the affinity between the layered silicate and the organic polymer is increased, and the layered silicate is finely dispersed more uniformly in the organic polymer. be able to.

Examples of the cationic surfactant include, but are not particularly limited to, quaternary ammonium salts, quaternary phosphonium salts, and the like. Hydrophobic), a quaternary ammonium salt containing at least one alkyl group having 6 or more carbon atoms (an alkyl ammonium salt having 6 or more carbon atoms) is preferably used. These cationic surfactants may be used alone or in combination of two or more.

The quaternary ammonium salt is not particularly limited, and examples thereof include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, and distearyl. Examples include dibenzylammonium salts, N-polyoxyethylene-N-lauryl-N, N-dimethylammonium salts, and polyoxypropylene diethylammonium salts. These quaternary ammonium salts may be used alone or in combination of two or more.

Examples of the quaternary phosphonium salt include, but are not particularly limited to, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, and dioctylmethylphosphonium salt. Stearyl dimethyl phosphonium salt, distearyl dibenzyl phosphonium salt and the like can be mentioned. These quaternary phosphonium salts may be used alone or in combination of two or more.

The layered silicate can be improved in dispersibility in an organic polymer by performing such a chemical treatment (organization treatment).

The layered silicate preferably has an average interlayer distance of the (001) plane measured by a wide-angle X-ray diffraction measurement method of 3 nm or more, and more preferably partially or entirely dispersed in 5 layers or less. Means that the average interlayer distance is 6 nm or more, and a part or the whole is dispersed in 5 layers or less. Incidentally, the average interlayer distance of the layered silicate referred to in the present invention means the average interlayer distance in the case of a layer of fine flake crystals of the layered silicate, by X-ray diffraction peak and transmission electron microscopy, That is, it can be calculated by the wide-angle X-ray diffraction measurement method. Further, the dispersion state of the layered silicate is observed by a transmission electron microscope at a magnification of 50,000 to 100,000 times, and among the number (X) of the laminated aggregates of the layered silicate that can be observed in a certain area, The number (Y) of the layered aggregates dispersed in 5 layers or less can be counted and calculated by the following formula (2).
Ratio (%) dispersed in 5 layers or less = (Y / X) × 100 (2)

Originally, when the layered molecules of the layered silicate, which is a laminated body of several tens of layers, are separated and dispersed, the interaction between the crystal flake layers of the layered silicate is weakened so as to be almost negligible, and the crystal flakes are formed in the organic polymer. It becomes a finely dispersed state with a constant interval and is stabilized. A cured product of the curable composition obtained by blending and dispersing such a layered silicate in an organic polymer exhibits various properties such as extremely excellent weather resistance, excellent flame retardancy, and mechanical strength. Will do. Further, when the average interlayer distance between the layered silicate crystal flake layers is 3 nm or more, preferably 6 nm or more, the layered silicate crystal flake layers separate from each other, and the interaction between the layered silicate crystal flake layers is reduced. Since it is almost negligibly weak, there is an advantage that the dispersion state of the crystal flakes constituting the layered silicate in the organic polymer proceeds in the direction of stabilization of crushing.

In addition, the fact that part or all of the layered silicate is dispersed in five or less layers means that part or all of the layered molecules of the layered silicate, which is essentially a laminate of several tens of layers, are peeled and widely dispersed. This also means that the interaction between the crystal flake layers of the layered silicate is weakened, and the same effect as described above can be obtained. Further, the fact that part or all of the layered silicate is dispersed in 5 layers or less means that, specifically, it is preferable that 10% or more of the layered silicate is dispersed in 5 layers or less. This means that 20% or more of the layered silicate is dispersed in 5 layers or less.

The number of layers of the layered silicate is preferably 5 or less, more preferably 3 or less, still more preferably a single layer (laminate). That is.

In the curable composition of the present invention, the state in which the average interlayer distance between the crystal flake layers of the layered silicate is 3 nm or more, and part or all of the layered silicate is dispersed in 5 layers or less, that is, the organic layer If the layered silicate is highly dispersed in the polymer, the interface area between the organic polymer and the layered silicate increases, and the average adjacent distance between the crystal flakes of the layered silicate decreases.

When the interface area between the organic polymer and the layered silicate increases, the degree of constraint of the organic polymer on the surface of the layered silicate increases, and the cured product of the curable composition has improved mechanical strength such as elastic modulus. Further, the baffle effect of the layered silicate suppresses bleed-out of a compounding agent (additive) such as a light stabilizer or an ultraviolet absorber in the curable composition, and the ultraviolet shielding effect of the layered silicate. Thereby, the weather resistance of the cured product of the curable composition is further improved.

Various stirrers and kneaders can be used to disperse (blend) the layered silicate with respect to the organic polymer. If dispersion is difficult, use a kneader to which a high shearing force such as a three-roller is applied. Is preferred.

The curable composition of the present invention further contains 0.1 to 20 parts by weight of a light stabilizer and / or 0.1 to 20 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of the organic polymer. And more preferably 1 to 10 parts by weight of a light stabilizer and / or 1 to 10 parts by weight of an ultraviolet absorber. By blending a light stabilizer and / or an ultraviolet absorber with the organic polymer, the cured product of the curable composition exhibits extremely excellent weather resistance. This is because the light stabilizer and / or the ultraviolet absorber hardly bleeds out and volatilizes from the cured product of the curable composition when used in combination with the above-mentioned layered silicate, and is stable in the cured product for a long time. It is because it is held.

When the compounding amount of the light stabilizer is less than 0.1 part by weight and / or the compounding amount of the ultraviolet absorber is less than 0.1 part by weight based on 100 parts by weight of the organic polymer, the cured product of the curable composition In some cases, the effect of improving the weather resistance may be poor, and if the amount of the light stabilizer exceeds 20 parts by weight and / or the amount of the ultraviolet absorber exceeds 20 parts by weight based on 100 parts by weight of the organic polymer. In addition, the curable composition may be colored, and the appearance as a sealant or an adhesive may be impaired.

The light stabilizer is not particularly limited, and includes, for example, various known light stabilizers such as a hindered amine light stabilizer. Agents are preferably used. These light stabilizers may be used alone or in combination of two or more.

Examples of the hindered amine light stabilizer include, but are not particularly limited to, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (2 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2- (3,5-di-t-butyl-4-) Bis (1,2,2,6,6-pentamethyl-4-piperidyl) hydroxybenzyl) -2-n-butylmalonate; These hindered amine light stabilizers may be used alone or in combination of two or more.

The ultraviolet absorber is not particularly limited, and includes, for example, various known ultraviolet absorbers such as a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber. For this reason, a benzotriazole-based ultraviolet absorber is preferably used. These ultraviolet absorbers may be used alone or in combination of two or more.

Although it does not specifically limit as said benzotriazole type ultraviolet absorber, For example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2) -Hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, and the like, And the like. These benzotriazole-based ultraviolet absorbers may be used alone or in combination of two or more.

In the curable composition of the present invention, if necessary within a range not hindering the achievement of the object of the present invention, in order to further improve flame retardancy, for example, metal hydroxide, metal oxide, melamine derivative, benzo A non-halogen flame retardant such as oxazine or a flame retardant aid such as carbon black, fluororesin, silicone oil, or silicone-acrylic composite rubber may be blended. These non-halogen flame retardants and / or flame retardant auxiliaries may be used alone or in combination of two or more.

The curable composition of the present invention is characterized in that, in a combustion test based on ASTM E 1354, a cured residue obtained by heating and burning under a radiation heating condition of 50 kW / m ² for 30 minutes is 0.1 cm. It is preferable that the yield point stress when compressed at a speed of / sec is 4.9 kPa or more.

If the yield point stress of the cured product of the curable composition is less than 4.9 kPa, a shape retaining force cannot be obtained in the event of a fire, so that the adhesive comprising the curable composition of the present invention may be applied to, for example, a tile or the like. When used for adhesion of an adherend, the adherend may easily fall.

Next, the sealing material and the adhesive of the present invention are prepared using the above-described curable composition of the present invention.

The sealing material and the adhesive of the present invention, in addition to the curable composition of the present invention, if necessary within a range not hindering the achievement of the object of the present invention, for example, a curing catalyst such as a silanol condensation catalyst, a plasticizer (Softening agent), one or two of various compounding agents (additives) such as an adhesion improver, a dehydrating agent, a filler, an anti-sagging agent, an antioxidant (anti-aging agent), a coloring agent, a fragrance, and an organic solvent. More than one kind may be blended.

The silanol condensation catalyst as a curing catalyst is used to promote the moisture curing reaction of the curable composition of the present invention containing the organic polymer as a main component, and specific examples thereof are particularly limited. Although not intended, for example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), Tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide; titanate compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate; amine salts such as dibutylamine-2-ethylhexoate; and others Acid catalysts and basic catalysts That. These silanol condensation catalysts may be used alone or in combination of two or more. In order to further increase the curing speed, for example, one or more of diaryldialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane may be used in combination.

Examples of the plasticizer include, but are not limited to, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate; aliphatic dibasic acids such as dioctyl adipate, isodecyl succinate and dibutyl sebacate Esters; glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; phosphate esters such as trioctyl phosphate and octyl diphenyl phosphate; epoxidized soybean oil Epoxidized plasticizers such as epoxidized linseed oil; glycols such as polyethylene glycol and polypropylene glycol; chlorinated paraffin, polybutadiene, and isoparaffin. Since it is excellent in all resistance and resistance to bleeding out and the like, a number average molecular weight of polypropylene glycol of 500 to 30,000 is preferably used. These plasticizers may be used alone or in combination of two or more.

The amount of the plasticizer is not particularly limited, but is preferably not more than 80 parts by weight based on 100 parts by weight of the organic polymer constituting the curable composition of the present invention. If the amount of the plasticizer is more than 80 parts by weight based on 100 parts by weight of the organic polymer, a problem may occur in the coating properties of the cured product of the sealing material and the adhesive.

The adhesion improver is not particularly limited, but examples thereof include a compound having an amino group and an alkoxysilyl group in one molecule, and a bissilyl compound. These adhesiveness improvers may be used alone or in combination of two or more.

The compound having an amino group and an alkoxysilyl group in one molecule is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyltriethoxysilane. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Ethoxysilane, 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- (t Methoxysilyl) propyl] hexamethylenediamine, N, N'-bis- [3- (triethoxysilyl) propyl] hexamethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] hexamethylenediamine N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (triethoxysilyl) )) Propyl] ethylenediamine, N, N-bis- [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] hexamethylenediamine, N, N-bis -[3- (triethoxysilyl) propyl] hexamethylenediamine, N, N- Su- [3- (trimethoxysilyl) propyl] amine, N, N-bis- [3- (triethoxysilyl) propyl] amine, N, N-bis- [3- (methyldimethoxysilyl) propyl] amine and the like Is mentioned. These compounds having an amino group and an alkoxysilyl group in one molecule may be used alone or in combination of two or more.

Further, the bissilyl compound is not particularly limited, and for example, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (tri Ethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N '-Bis- [3- (triethoxysilyl) propyl] hexamethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] hexamylenediamine, N, N-bis- [3- (tri Methoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (triethoxysilyl) propyl] ethylenediamine N, N-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (triethoxy) Silyl) propyl] hexamethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (trimethoxysilyl) propyl] amine, N, N- Bis- [3- (triethoxysilyl) propyl] amine, N, N-bis- [3- (methyldimethoxysilyl) propyl] amine and the like can be mentioned. These bissilyl compounds may be used alone or in combination of two or more.

The dehydrating agent is not particularly limited, but includes, for example, vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethylsilane And silane compounds such as diphenyldimethoxysilane, and hydrolysable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more.

The filler is not particularly limited, but includes, for example, magnesium carbonate, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, clay, talc, mica, carbon black, titanium oxide, glass balloon, wollastonite, carbon Fiber, rubber powder, cement and the like can be mentioned. These fillers may be used alone or in combination of two or more.

Examples of the anti-sagging agent are not particularly limited, and examples thereof include hydrogenated castor oil, fatty acid bisamide, and fumed silica. These anti-sagging agents may be used alone or in combination of two or more.

The organic solvent is not particularly limited, and examples thereof include a synthetic isoparaffinic solvent having a flash point of 40 ° C. or higher. These organic solvents may be used alone or in combination of two or more.

The method for producing the sealing material and the adhesive of the present invention is not particularly limited, and for example, a universal mixer, a kneader, a two-roller, a three-roller, a known stirrer or a kneader such as an extruder may be used alone or In combination, after preparing the curable composition of the present invention in advance, a predetermined amount of the curable composition may be added, if necessary, a curing catalyst such as a silanol condensation catalyst, a plasticizer, an adhesion improver, and a dehydration agent. Agents, fillers, anti-sagging agents, antioxidants, coloring agents, fragrances, compounding predetermined amounts of various compounding agents such as organic solvents, and kneading them uniformly, may be used as a sealing material or an adhesive, The curable composition of the present invention and the respective predetermined amounts of the components constituting the sealing material and the adhesive may be mixed together and uniformly kneaded to form a sealing material or an adhesive. The above-mentioned production is preferably performed in a sealed system under reduced pressure or an atmosphere of an inert gas such as nitrogen gas in order to prevent moisture from entering from the outside.

(Action)
The curable composition of the present invention is characterized in that a specific amount of calcium carbonate having a specific BET specific surface area or a specific average particle diameter is mixed with an organic polymer containing at least one crosslinkable hydrolyzable silyl group. Therefore, the cured product is less likely to crack on the surface even when exposed to the outdoors, and exhibits excellent weather resistance.

Further, the curable composition of the present invention further comprises a specific amount of a layered silicate with respect to the above-mentioned organic polymer, whereby the cured product exhibits more excellent weather resistance and has excellent difficulty. Flammability is also exhibited.

In addition, the curable composition of the present invention further comprises a specific amount of a light stabilizer and / or a specific amount of an ultraviolet absorber with respect to the organic polymer, so that the cured product has extremely excellent weather resistance. It expresses sex.

Further, the curable composition of the present invention, by using an organic polymer whose main chain consists essentially of a polyether-based polymer and / or a vinyl-based polymer as the organic polymer, It exhibits excellent rubber elasticity and water resistance.

Since the sealing material and the adhesive of the present invention are composed of the curable composition of the present invention, the cured product exhibits various properties such as excellent weather resistance, flame retardancy, rubber elasticity, and water resistance.

As described above, the curable composition of the present invention can be suitably used as a sealant or an adhesive because it can be cured by moisture at room temperature to obtain a cured product exhibiting excellent weather resistance.

Further, since the sealing material and the adhesive of the present invention are prepared using the curable composition of the present invention, the cured product has various properties such as excellent weather resistance, flame retardancy, rubber elasticity, and water resistance. It exhibits performance, and is suitably used for various applications as a sealing material and an adhesive for outdoor use as well as for indoor use.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the examples and comparative examples, the following raw materials were used. In addition, the BET specific surface area and the average particle diameter of calcium carbonate are values measured by the above-described measuring methods, respectively. Calcium carbonate and titanium oxide which had been heated and dehydrated at 110 ° C. in advance were used.
1. Organic polymer (modified silicone polymer) (1) Trade name “MS Polymer S-203” (bifunctional polymer: terminal structure —Si (CH ₃ ) (OCH ₃ ) ₂ , number average molecular weight: 20,000, Kanegafuchi Chemical Industry (2) Trade name “MS Polymer S-303” (trifunctional polymer: terminal structure—Si (OCH ₃ ) ₃ , number average molecular weight: 20,000, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) Calcium carbonate (1) Calcium carbonate having a BET specific surface area of 14.0 m ² / g and an average particle diameter of 1.0 μm (trade name “Shirayuka A” manufactured by Shiraishi Industry Co., Ltd.) (2) BET specific surface area of 6 .5m a ² / g, an average calcium carbonate particle diameter of 0.5 [mu] m (trade name "Tsunekkusu E", manufactured by Shiraishi Kogyo Co., Ltd.) (3) BET specific surface area of 34.0m ² / g, average particle Calcium carbonate having a diameter of 0.05 μm (trade name “Shirayuka AA”, manufactured by Shiraishi Industry Co., Ltd.) (4) Calcium carbonate having a BET specific surface area of 1.5 m ² / g and an average particle diameter of 3.2 μm ( 2. Product name "Whiteton SSB Blue", manufactured by Shiraishi Calcium Co.) 3. Layered silicate Layered silicate organically treated with polyoxypropylene diethyl quaternary ammonium salt (trade name “Somasif MPE-100”, manufactured by Corp Chemical) 4. Light stabilizer Hindered amine light stabilizer (trade name "Tinuvin 770", manufactured by Ciba Specialty Chemicals) 5. UV absorber benzotriazole-based UV absorber (trade name “Tinuvin 327”, manufactured by Ciba Specialty Chemicals) Other compounding agents (1) Silanol condensation catalyst dibutyltin dilaurate (2) Plasticizer polypropylene glycol (trade name "Diol 3000", number average molecular weight: 3,000, manufactured by Mitsui Chemicals, Inc.) (3) Adhesion improver N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane (trade name "KBM603", manufactured by Shin-Etsu Chemical Co., Ltd.) (4) Dehydrating agent vinyltrimethoxysilane (trade name "Sila Ace S210", manufactured by Chisso Corporation) (5) Filler Titanium oxide (trade name "Taipaek CR-90", manufactured by Ishihara Sangyo Co., Ltd.)

(Examples 1 to 4) and (Comparative Examples 1 to 3)
A composition having a composition shown in Table 1 (composition unit: parts by weight) is supplied to a stirred kneader kneaded so as to prevent moisture from entering from the outside, and is uniformly kneaded under reduced pressure to obtain a sealing material and / or A curable composition that can be used as an adhesive was prepared.

The average interlayer distance of the layered silicate and the dispersed state of the layered silicate in the curable compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were confirmed by the following methods. The results were as shown in Table 1.

[Average interlayer distance of layered silicate] 2θ of the diffraction peak obtained from the diffraction of the laminated surface of the layered silicate in the curable composition using an X-ray diffractometer (trade name “RINT1100”, manufactured by Rigaku Corporation). Was measured, and the (001) interplanar spacing (d) of the layered silicate was calculated using the following black diffraction equation (3), and the average interlayer distance was evaluated according to the following criteria using d as the average interlayer distance. .
λ = 2dsinθ (3)
(Where d represents the plane spacing of the layered silicate, θ represents the diffraction angle, and λ is 0.154)
Criteria ○ ‥‥ The average interlayer distance (d) of the layered silicate was 3 nm or more.
× ‥‥ The average interlayer distance (d) of the layered silicate was less than 3 nm.

[Dispersion state of layered silicate] The dispersion state of the layered silicate in the curable composition was observed with a transmission electron microscope (TEM, trade name "JEM-1200EX II", manufactured by JEOL Ltd.) photograph, and the following judgment was made. The dispersion state was evaluated according to the standard.
-Judgment criteria ○ ‥‥ Layered silicate was present in 5 layers or less.
× ‥‥ Layered silicate was present in more than 5 layers.

Next, the weatherability of the curable compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated by the following method. The results were as shown in Table 1.

(Weather resistance evaluation method)
The curable composition is applied to a stainless plate (width: 50 mm, length: 150 mm, thickness: 1 mm) so as to have a thickness of 0.5 mm, and left in an atmosphere of 20 ° C.-60% RH for 7 days. Cured and cured. Next, the cured product was irradiated with light under the following conditions for 150 hours and 400 hours, and then the surface of the cured product was visually observed, and the weather resistance of the cured product was evaluated according to the following criteria.
-Light irradiation conditions Test equipment: Trade name "Ice Par UV Tester" (Model: SUV-F11, manufactured by Iwasaki Electric Co., Ltd.)
Irradiation intensity: 100 mW / cm ²
Limited wavelength: 295-450 nm
Black panel temperature: 63 ° C
Irradiation distance (distance between light source and cured product): 235 mm
Irradiation time: 150 hours and 400 hours Criteria ○ ‥‥ No cracks were observed on the surface of the cured product.
X: Cracks were observed on the surface of the cured product.

As is clear from Table 1, the cured products of the curable compositions of Examples 1 to 4 according to the present invention all exhibited excellent weather resistance. On the other hand, the cured product of the curable composition of Comparative Example 1 using calcium carbonate having a BET specific surface area of more than 15 m ² / g and an average particle size of less than 0.3 μm was irradiated with light for 400 hours. Cracking was observed on the surface of the cured product later, and the weather resistance was poor. The cured product of the curable composition of Comparative Example 2 using calcium carbonate having a BET specific surface area of less than 2 m ² / g and having an average particle size of more than 2 μm, and a BET specific surface area of calcium carbonate of 2 Although the average particle diameter was in the range of 0.3 to ² μm, the blending amount of calcium carbonate with respect to 100 parts by weight of the organic polymer (modified silicone polymer) exceeded 200 parts by weight. In each of the cured products of the curable composition of Comparative Example 3, the dispersion of calcium carbonate in the organic polymer was poor, so that calcium carbonate was precipitated on the surface of the cured product.

According to the present invention, it is possible to provide a curable composition that cures at room temperature by reacting with moisture in the air, and a sealing material and an adhesive using the curable composition.

It is a schematic diagram which shows the crystal surface (A) and crystal end surface (B) of a layered silicate.

Claims (7)

It is characterized in that 30 to 200 parts by weight of calcium carbonate having a BET specific surface area of ² to 15 m ² / g is mixed with 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. Curable composition. The composition is characterized in that 30 to 200 parts by weight of calcium carbonate having an average particle diameter of 0.3 to 2 μm is blended with respect to 100 parts by weight of an organic polymer containing at least one crosslinkable hydrolyzable silyl group. Curable composition. The curable composition according to claim 1, further comprising 0.1 to 100 parts by weight of a layered silicate. The light stabilizer according to any one of claims 1 to 3, further comprising 0.1 to 20 parts by weight of a light stabilizer and / or 0.1 to 20 parts by weight of an ultraviolet absorber. Curable composition. The curable composition according to any one of claims 1 to 4, wherein the main chain of the organic polymer consists essentially of a polyether polymer and / or a vinyl polymer. A sealing material comprising the curable composition according to any one of claims 1 to 5. An adhesive comprising the curable composition according to any one of claims 1 to 5.

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