JPH11193343A - Room temperature curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material or the like which hardly causes time-dependent contamination on the surface of a cured product without using a surface protective agent and exhibits excellent physical properties after curing. A room temperature curable composition is provided. The main chain is essentially a polyether,
At least one terminal has a crosslinkable hydrolyzable silyl group and has a number average molecular weight of 4,000 to 30,000 per 100 parts by weight of a polyether-based polymer.
It contains 0.1 to 20 parts by weight of an amine compound having at least two amino groups and having a melting point of 10 to 200 ° C or a fatty acid ester of polyglycerin having a polymerization degree of 2 to 5 and a silanol condensation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a room temperature curable composition suitable mainly as a sealing material and the like.

[0002]

2. Description of the Related Art Conventionally, a polymer which is cured by reacting with moisture in the atmosphere and is converted into an elastomer has been widely used as a sealing material, an adhesive or the like (hereinafter, simply referred to as "sealing material"). As a sealing material using such a moisture-curable polymer, for example, JP-B-61-18852.
Japanese Patent Application Laid-Open Publication No. H11-163873 discloses that “a silyl ether group represented by a specific general formula is present at at least one terminal, the main chain is essentially a propylene oxide polymer, and the molecular weight is 6300 to 15
Room temperature-curable sealant (sealant) composition containing a novel polyether having a molecular weight of 000 as an active ingredient.

[0003] However, the sealing material containing polyether as a main component as described in the above proposal, for example, when used as a joint of an outer wall of a building, the surface thereof becomes dusty or exhaust gas with the passage of time (aging). There is a major problem in appearance that it is contaminated by the water and becomes unsightly.

To cope with the above problem, for example, Japanese Patent Publication No. 60-8024 discloses a polymer having a molecular weight of at least one hydrolyzable silicon group per molecule of 300 to 300.
Polyester, polyether, polystyrene, poly-α-methylstyrene, polybutadiene, alkyd resin, polychloroprene, and butadiene having a molecular weight of 300 to 15,000 per 100 parts by weight of the organic polymer of 15,000.
Curable compositions containing 1 to 150 parts by weight of a polymer plasticizer selected from the group consisting of acrylonitrile copolymers "have been proposed.

[0005] However, the curable composition containing a high-molecular plasticizer in place of the ordinary low-molecular plasticizer also has a sufficient effect of preventing sedimentation and slump, although it has an effect of preventing sedimentation and slump. It does not have an effect, and in the end, in order to prevent the contamination of the surface of the sealing material with the passage of time, a surface protective agent such as a coating agent or a paint is applied to the surface of the sealing material or the like, and the surface of the sealing material or the like is coated. Protection is often adopted.

However, in the case of the method of applying the surface protective agent, the work steps are complicated and the cost is increased, and the problem that the surface of the sealing material or the like is contaminated with time is drastically solved. It does not help.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems without using a surface protective agent.
It is an object of the present invention to provide a room-temperature curable composition which is less likely to cause contamination with time on the surface of a cured product and is suitable for obtaining a sealing material or the like exhibiting excellent physical properties after curing.

[0008]

The room-temperature-curable composition of the invention according to claim 1 (hereinafter referred to as "first invention") comprises:
The main chain is essentially a polyether, has a crosslinkable hydrolyzable silyl group at at least one terminal, and has a number average molecular weight of 4,000 to 30,000 based on 100 parts by weight of a polyether polymer. It is characterized by comprising 0.1 to 20 parts by weight of an amine compound having two or more amino groups in the molecule and having a melting point of 10 to 200 ° C., and a silanol condensation catalyst.

The room-temperature-curable composition of the first invention has two or more amino groups in one molecule and has a melting point of 10 to 200 ° C., preferably 100 parts by weight of the above-mentioned polyether polymer. 20-140 ° C., an amine compound (hereinafter, referred to as
(Hereinafter simply referred to as "amine compound") in an amount of 0.1 to 20 parts by weight and a silanol condensation catalyst.

When the number of amino groups in the above-mentioned amine compound is less than 2 in one molecule, the number of residual amino groups in the resulting room-temperature-curable composition is reduced, the hydrophilicity is reduced, and the sealing material is reduced. Etc., the effect of preventing surface contamination may be insufficient.

If the melting point of the amine compound is less than 10 ° C., the cured product such as a sealing material easily bleeds out to the surface thereof, causing surface contamination of the sealing material and the like and contamination of the adherend. On the contrary, when the melting point of the amine compound exceeds 200 ° C., mixing with the polyether polymer becomes difficult, and a mixing method such as melting by heating at a high temperature or dissolving with a large amount of an organic solvent is used. This is necessary, which is not preferable in terms of process and performance.

Specific examples of the amine compound having two or more amino groups in one molecule and having a melting point of 10 to 200 ° C. are not particularly limited.
H ₃ (CH ₂ ) ₁₇ NH (CH ₂ ) ₃ NH ₂ (melting point 48
° C) and m-phenylenediamine (melting point 63 ° C) and the like are preferably used. The above amine compounds may be used alone or in combination of two or more.

When the content of the amine compound is less than 0.1 part by weight based on 100 parts by weight of the polyether polymer, the hydrophilicity of the resulting room-temperature curable composition is reduced, and surface contamination of a sealing material or the like is caused. On the contrary, if the content of the amine compound exceeds 20 parts by weight with respect to 100 parts by weight of the polyether-based polymer, the effect corresponding to the content cannot be expected. Without
There is a possibility that physical properties of the sealing material and the like may be adversely affected.

Further, the invention according to claim 2 (hereinafter referred to as “second
Room temperature-curable composition of the present invention) is essentially a polyether, has a crosslinkable hydrolyzable silyl group at at least one terminal, and has a number average molecular weight of 400.
It is characterized by containing 0.1 to 20 parts by weight of a fatty acid ester of polyglycerin having a degree of polymerization of 2 to 5 and a silanol condensation catalyst with respect to 100 parts by weight of a polyether polymer of 0 to 30,000. .

The room temperature curable composition of the second invention has a degree of polymerization of 2 with respect to 100 parts by weight of the above-mentioned polyether polymer.
And 0.1 to 20 parts by weight of a fatty acid ester of polyglycerin (hereinafter simply referred to as "fatty acid ester") and a silanol condensation catalyst.

If the degree of polymerization of the polyglycerol used for the fatty acid ester exceeds 6, the effect of preventing surface contamination commensurate with the cost cannot be obtained despite the high cost, and the practicality is poor.

The polyglycerol having a degree of polymerization of 2 to 5 may be used alone or in combination of two or more.

The fatty acid used in the above fatty acid ester is not particularly limited, and includes, for example, a saturated or unsaturated fatty acid having 10 to 20 carbon atoms.
It is preferably used.

When the fatty acid has less than 10 carbon atoms,
The resulting fatty acid ester may be poorly compatible with the polyether-based polymer. Conversely, if the fatty acid has more than 20 carbon atoms, the surface of a sealing material or the like using the resulting room-temperature-curable composition may be damaged. In some cases, the amount of the liquid substance increases, and the surface is rather easily contaminated.

Specific examples of the above-mentioned fatty acids having 10 to 20 carbon atoms are not particularly limited. For example, saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and arachinic acid, and oleic acid And unsaturated fatty acids such as linoleic acid, linolenic acid, arachidonic acid, and stearic acid. The above fatty acids may be used alone or in combination of two or more.

The degree of esterification of a fatty acid ester obtained from polyglycerol having a degree of polymerization of 2 to 5 and a fatty acid is as follows:
Although not particularly limited, a monoester or a diester is preferable.

When the degree of esterification of the fatty acid ester is equal to or higher than the triester, the number of residual hydroxyl groups in the obtained room temperature curable composition decreases, the hydrophilicity decreases, and the effect of preventing surface contamination of a sealing material or the like is impaired. May be sufficient.

Specific examples of the fatty acid ester of polyglycerin having a degree of polymerization of 2 to 5 are not particularly limited. For example, diglycerin laurate, diglycerin stearate, diglycerin oleate, diglycerin capri Rate, diglycerin monolaurate, diglycerin monostearate, diglycerin monooleate,
Tetraglycerin stearate, tetraglycerin oleate and the like are mentioned, and are preferably used. The above fatty acid esters may be used alone or in combination of two or more.

When the content of the fatty acid ester is less than 0.1 part by weight based on 100 parts by weight of the polyether polymer, the hydrophilicity of the resulting room-temperature-curable composition decreases,
In some cases, the effect of preventing surface contamination of a sealing material or the like cannot be sufficiently obtained. Conversely, if the content of the fatty acid ester exceeds 100 parts by weight with respect to 100 parts by weight of the polyether-based polymer, an effect corresponding to the added amount is expected. Despite not being able to,
There is a possibility that physical properties of the sealing material and the like may be adversely affected.

The invention according to claim 3 (hereinafter referred to as “third
Room temperature-curable composition of the present invention) is essentially a polyether, has a crosslinkable hydrolyzable silyl group at at least one terminal, and has a number average molecular weight of 400.
It is characterized by comprising 0.1 to 20 parts by weight of a nonionic surfactant having a melting point of 10 to 200 ° C. and a silanol condensation catalyst with respect to 100 parts by weight of a polyether-based polymer of 0 to 30,000. I do. The room temperature-curable composition of the third invention is a nonionic surfactant having a melting point of 10 to 200 ° C. (hereinafter simply referred to as “nonionic surfactant”) based on 100 parts by weight of the above-mentioned polyether-based polymer. Written as
It contains 0.1 to 20 parts by weight and a silanol condensation catalyst.

When the melting point of the above nonionic surfactant is low, the leaching to the surface of the cured product becomes so severe that the base material and the coating film are stained, and it is difficult to maintain the antifouling property for a long time. If the temperature is too high, it is difficult to mix with the polyether polymer, and the temperature is limited to 10 to 200 ° C, preferably 20 to 140 ° C, because melting at a high temperature or a large amount of solvent is required.

Examples of the nonionic surfactant having a melting point of 10 to 200 ° C. include sorbitan stearate (melting point: 60 ° C.) and sorbitan palmitate (melting point: 5
Sorbitan fatty acid ester-based surfactants such as glycerin monostearate (melting point: 65 ° C) and diglycerin stearate (melting point; 70 ° C); polyoxyethylene alkylamine ( (Melting point; 30 ° C.). The nonionic surfactants may be used alone or in combination of two or more.

Further, the room-temperature-curable composition of the fourth invention (hereinafter referred to as the "fourth invention") comprises the above-mentioned polyether polymer and a (meth) acrylate copolymer whose main chain is essentially a (meth) acrylate ester. Has at least one crosslinkable hydrolyzable silyl group, and has a number average molecular weight of 6,000 to 300.
0.1 to 20 parts by weight of a nonionic surfactant having a melting point of 10 to 200 ° C. is contained with respect to 100 parts by weight of the total amount of the (meth) acrylic acid ester-based polymer which is 00.

The main chain is essentially a (meth) acrylate copolymer having at least one crosslinkable hydrolyzable silyl group (hereinafter referred to as “(meth) acrylate”).
Acrylate-based polymer ”) is, for example, a polymer obtained by the following methods (1) to (4). (1) A method of reacting a (meth) acrylate copolymer having an allyl group with a silicon hydride compound represented by the following general formula (1) in the presence of a Group VIII transition metal (JP-A-54 No. 36395).

Embedded image (Wherein, X represents a halogen atom, an alkoxy group, an acyloxy group or a ketoxime group, R represents a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, and n represents an integer of 0, 1 or 2) (2) A method of copolymerizing a (meth) acrylate in the presence of a (meth) acrylate containing an alkoxysilyl group and a chain transfer agent containing a mercapto group (JP-A-57-179210) . (3) A method of copolymerizing a (meth) acrylic ester in the presence of a bifunctional radical polymer compound and a mercaptan containing an alkoxysilyl group as a chain transfer agent (JP-A-59-784220). (4) A method of polymerizing using an azobis nitrile compound containing an alkoxysilyl group as a polymerization initiator using a (meth) acrylic acid ester (Japanese Patent Application Laid-Open No. 60-23405).

Here, the (meth) acrylate means alkyl acrylate or alkyl methacrylate.

Among the above (meth) acrylic ester-based polymers, the main chain is composed of an alkyl ester of an alkyl group having 1 to 12 carbon atoms and an alkyl ester of a methacrylic acid having 1 to 14 carbon atoms. The polymer containing the polymer as a main component is preferred. Further, as a crosslinkable hydrolyzable silyl group, an alkoxysilyl group such as a methoxysilyl group and an ethoxysilyl group is preferable because no harmful by-product is generated after the reaction. The number average molecular weight of the (meth) acrylate polymer is 6
It is limited to 000-30000. Number average molecular weight is 60
If it is less than 00, the tackiness (stickiness) of the cured product becomes too large, and if the number average molecular weight exceeds 30,000, the compatibility with the polyether polymer decreases, and the effect of improving the weather resistance becomes insufficient.

The mixing ratio of the polyether polymer and the (meth) acrylate polymer is 0.1 to 0.1 parts by weight of the (meth) acrylate polymer per 100 parts by weight of the polyether polymer. A mixing ratio of 100 parts by weight is preferable. When the amount of the polymer (B) is less than 0.1 part by weight,
If the effect of improving the weather resistance is reduced, and if it exceeds 100 parts by weight, the curability and the elongation of the cured product are reduced. More preferably, it is 0.5 to 80 parts by weight.

The room-temperature-curable compositions of the first to fourth inventions may, if necessary, besides the above-mentioned essential components, as long as they do not impair the achievement of the object of the present invention. One or more matting agents for matting may be contained. The matting agent is not particularly limited, for example, glass beads,
Organic or inorganic having an average particle size of about 10 to 80 μm, such as silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, vinylidene chloride balloons, and acrylic balloons. One or more of these are suitably used, and among them, a glass balloon which hardly lowers the extensibility of a cured product of a room temperature-curable composition is more preferably used.

The room-temperature-curable composition according to the invention described in claim 5 (hereinafter referred to as “fifth invention”) has a main chain consisting essentially of a polyether, and has at least one terminal crosslinkable hydrolysis. Having a hydrophilic silyl group and a number average molecular weight of 4000
0.1 to 20 parts by weight of a nonionic surfactant having a melting point of 10 to 200 ° C. and 2 to 30 parts of a matting agent having an average particle size of 10 to 80 μm with respect to 100 parts by weight of a polyether polymer having a particle size of 10 to 80 ° C. Parts by weight.

The matting agent is not particularly restricted but includes, for example, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloon, glass Average particle size of balloon, silica balloon, vinylidene chloride balloon, acrylic balloon, etc. 10
Organic or inorganic matting agent of about ~ 80 μm,
One or more of these are preferably used,
Among them, glass balloons that hardly lower the extensibility of the cured product of the room temperature curable composition are more preferably used.

The above average particle size must be 10 μm to 80 μm. When the average particle size is less than 10 μm, a sufficient matting effect cannot be obtained, and when the average particle size exceeds 80 μm, the elongation after the room temperature curable composition is cured becomes small.
2 matting agents per 100 parts by weight of polyether polymer
-30 parts by weight. 2 matting agents
If the amount is less than the weight part, a sufficient matting effect cannot be obtained and 3
If the amount exceeds 0 parts by weight, the elongation after the room temperature curable composition is cured becomes small.

The room-temperature-curable compositions according to the first to fifth aspects of the present invention have a main chain essentially composed of polyether, have a crosslinkable hydrolyzable silyl group at at least one terminal, and have a number average molecular weight. Is 4000 to 30,000 (hereinafter simply referred to as “polyether polymer”).
Described below). In addition, in the room temperature curable compositions according to the first to third inventions and the fifth invention, a polyether-based polymer constitutes a main component.

The polyether-based polymer of the first to fifth inventions is not particularly limited.
A polyoxyalkylene having an allyl group at the terminal
It is a polymer obtained by reacting with a silicon hydride compound represented by the following general formula (2) in the presence of a Group II transition metal.

[0039]

Embedded image (Wherein, X represents a halogen atom, an alkoxy group, an acyloxy group or a ketoxime group, R represents a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, and n represents an integer of 0, 1 or 2)

The polyoxyalkylene constituting the main chain of the polyether polymer is not particularly limited, but includes, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene and the like. One or more kinds are suitably used. Among them,
When the resulting room-temperature-curable composition is used as a sealing material or the like, polyoxypropylene having excellent elasticity and water resistance is more preferably used.

The crosslinkable hydrolyzable silyl group contained in at least one terminal of the polyether polymer is not particularly limited. For example, an alkoxy group such as a methoxysilyl group or an ethoxysilyl group may be used. These include silyl groups, which are preferably used because they do not generate harmful by-products during the curing reaction.

The number average molecular weight of the polyether polymer must be 4000 to 30,000. When the number average molecular weight is less than 4,000, the extensibility of the obtained room temperature curable composition becomes insufficient, and when it exceeds 30,000, the viscosity of the polyether polymer becomes too high, and Worse.

The polyether polymer having a number average molecular weight of 10,000 to 30,000 and a molecular weight distribution (Mw / Mn) of 1.6 or less is used for handling the polyether polymer. It is preferable because the composition has good extensibility and the obtained cured product of the room-temperature curable composition also has excellent extensibility.

Specific examples of the polyether-based polymer are not particularly limited. For example, “MS Polymer” series and “Syril” series manufactured by Kaneka Chemical Co., Ltd., and Asahi Glass Co., Ltd. And the like, and are preferably used. The polyether polymer may be used alone,
Two or more types may be used in combination.

Among the above-mentioned various polyether polymers,
A room-temperature curable composition obtained by using a polyether polymer having a crosslinkable hydrolyzable silyl group containing an acrylic group at at least one terminal alone or in combination with another polyether polymer. Of the cured product such as a sealing material, it is difficult to generate cracks, and it is possible to prevent surface contamination and poor appearance due to the cracks. Further, since residual tack on the surface of the cured product of the room temperature curable composition is reduced, contaminants are hardly adhered, and it becomes possible to further suppress the surface of the sealing material and the like over time from being stained.

The silanol condensation catalyst contained in the room-temperature curable compositions according to the first to fifth inventions is not particularly limited, but examples thereof include titanates such as tetrabutyl titanate and tetrapropyl titanate. Tin carboxylate salts such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, tin octylate, tin naphthenate; reaction products of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate; aluminum trisacetyl Organoaluminum compounds such as acetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate ; And a conventionally known acidic catalyst or a basic catalyst as a silanol condensation catalyst such as lead octylate and the like, is preferably used.

The above silanol condensation catalyst may be used alone or in combination of two or more. The content of the silanol condensation catalyst with respect to the polyether polymer is not particularly limited, but the content of the silanol condensation catalyst is 0.1 to 100 parts by weight of the polyether polymer.
The amount is preferably from 5 to 5 parts by weight, more preferably from 0.1 to 5 parts by weight.
5 to 3 parts by weight.

If the content of the silanol condensation catalyst is less than 0.1 part by weight with respect to 100 parts by weight of the polyether polymer, a sufficient curing promoting effect may not be obtained. If the content of the silanol condensation catalyst is more than 5 parts by weight based on 100 parts by weight, the cost will increase even though the effect of accelerating curing is no longer improved.

The room-temperature-curable compositions according to the first to fifth aspects of the present invention have, in addition to the above-mentioned essential components, physical properties for improving tensile properties and the like, if necessary, within a range not to impair the achievement of the object of the present invention. Conditioner, dehydrating agent, inorganic filler, plasticizer (softener), coloring agent, antioxidant, ultraviolet absorber,
One or more of various additives such as a flame retardant and an organic solvent such as toluene and alcohol may be contained.

Examples of the physical property modifier include, but are not limited to, aminosilanes such as γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; γ-mercapto Various silane coupling agents such as mercaptosilanes such as propyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, and one or more of these are suitably used.

The dehydrating agent is not particularly restricted but includes, for example, vinylsilanes such as vinyltrimethoxysilane.
More than one species is preferably used.

The curing reaction of the polyether-based polymer used in the room-temperature curable compositions of the first to fifth inventions proceeds with moisture. Therefore, in order to prevent the room-temperature curable composition from thickening or gelling during storage due to a trace amount of water in the room-temperature curable composition, 1 to 5 parts by weight of the dehydrating agent is used per 100 parts by weight of the polyether-based polymer. It is preferable to include a part.

The inorganic filler is not particularly restricted but includes, for example, calcium carbonate, magnesium carbonate, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, clay, talc and the like. Alternatively, two or more types are suitably used.

Examples of the plasticizer (softening agent) include, but are not particularly limited to, phosphates such as tributyl phosphate and tricresyl phosphate; dibutyl phthalate;
Phthalate esters such as 2-ethylhexyl phthalate;
Fatty acid monobasic acid esters such as glycerin monooleate; fatty acid dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycols such as polypropylene glycol; and one or more of these are used. It is preferably used.

The colorant is not particularly limited, but may be, for example, carbon black, titanium oxide,
A petiole and the like can be mentioned, and one or more of these are suitably used.

The antioxidant is not particularly limited, and examples thereof include a hindered amine antioxidant and a hindered phenol antioxidant.
One or more of these are preferably used.

The method for producing the room-temperature-curable composition of the first to fifth inventions is not particularly limited. A predetermined amount of each component is weighed, and pre-mixed by a mixer such as a mixer or a kneader. Perform dehydration at room temperature or under heat under reduced pressure,
Next, the desired room temperature curable composition can be obtained by kneading the mixture uniformly using, for example, a three-roll mill.

(Function) The room temperature-curable composition of the first invention comprises:
The main chain is essentially a polyether, having a crosslinkable hydrolyzable silyl group at at least one terminal, and a polyether-based polymer having a number average molecular weight in a specific range as a main component, and one molecule. Since it has two or more amino groups in it and contains a specific amount of an amine compound having a melting point in a specific range, the cured product exhibits excellent weather resistance and physical properties,
Its surface has moderate hydrophilicity. Accordingly, it is suitable for obtaining a sealing material or the like which hardly generates contamination with time on the surface of the cured product and has excellent physical properties.

The room-temperature-curable composition of the second invention comprises the above-mentioned polyether-based polymer as a main component and a specific amount of a polyglycerol fatty acid ester having a specific degree of polymerization in a specific range. The cured product exhibits excellent weather resistance and physical properties, and its surface has moderate hydrophilicity. Therefore,
It is suitable for obtaining a sealing material or the like which hardly generates contamination over time on the surface of the cured product and has excellent physical properties.

Further, the room temperature-curable composition of the third invention comprises the above-mentioned polyether-based polymer as a main component and a specific amount of a nonionic surfactant having a melting point in a specific range. The cured product exhibits excellent weather resistance and physical properties,
Its surface has moderate hydrophilicity. Accordingly, it is suitable for obtaining a sealing material or the like which hardly generates contamination with time on the surface of the cured product and has excellent physical properties.

Further, the room temperature-curable composition of the fourth invention comprises:
Since the (meth) acrylate polymer is added, the weather resistance of the cured product is improved. As a result, light deterioration of the surface is suppressed, and fine cracks on the surface do not easily occur. Therefore, an increase in the area to which dirt adheres is suppressed, and the antifouling property is improved.

Further, since the room-temperature-curable composition of the fifth invention contains a matting agent having an average particle size of 10 μm to 80 μm, it does not cause so-called “shine” and has an appropriate gloss. Can be.

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, “parts” means “parts by weight”.

Example 1 (1) Preparation of Room-Temperature-Curable Composition “MS Polymer S2” (trade name) as a polyether polymer
03 "(number-average molecular weight: 10,000 to 20,000, manufactured by Kanegafuchi Chemical Co., Ltd.), 100 parts, CH ₃ (C
H ₂ ) ₁₇ NH (CH ₂ ) ₃ NH ₂ (melting point 48 ° C.), 2 parts,
Calcium carbonate (trade name "CCR", manufactured by Shiraishi Industry Co., Ltd.) 1
00 parts, titanium oxide (trade name “Taipaek CR-9”
0 ", manufactured by Ishihara Sangyo Co., Ltd.) and 20 parts of polypropylene glycol (trade name" Exenol 3020 ", manufactured by Asahi Glass Co., Ltd.)
After uniformly stirring and mixing 60 parts with a closed stirrer, the mixture was dehydrated by heating at 110 ° C. for 2 hours under reduced pressure. Then, after cooling to 30 ° C., 3 parts of vinylmethoxysilane, 2 parts of aminoethylaminopropyltrimethoxysilane, and 2 parts of dibutyltin dilaurate as a silanol condensation catalyst are added, and the mixture is uniformly stirred and mixed to obtain a room temperature curable composition. Obtained.

(2) Evaluation The performance of the room temperature curable composition obtained above (surface contamination,
Elongation) was evaluated by the following method. The results were as shown in Table 2.

Surface Stainability: After the room temperature-curable composition was cured into a sheet, it was exposed outdoors at a 30 ° angle on the south side, and the degree of decrease in the L value after 3 months of outdoor exposure to the initial elster (L value) was measured. The surface contamination was evaluated according to the criteria shown in Table 1 below.

[0067]

[Table 1]

Elongation: After the room temperature curable composition was cured into a sheet, it was punched out with a No. 3 dumbbell to prepare a test piece for measurement. Next, a tensile test was performed on the test piece for measurement in accordance with JIS K-6301 “Vulcanized Rubber Physical Test Method”, and the elongation at break (%) was determined.

Example 2 In preparing a room temperature curable composition, the content of the amine compound CH ₃ (CH ₂ ) ₁₇ NH (CH ₂ ) ₃ NH ₂ was set to 5 parts with respect to 100 parts of “MS polymer S203”. A room temperature curable composition was obtained in the same manner as in Example 1 except for the above.

Example 3 In preparing a room temperature-curable composition, diglycerin stearate (trade name “Liquemar S-71-D”) was used as a fatty acid ester instead of an amine compound, based on 100 parts of “MS polymer S203”. "
A room temperature curable composition was obtained in the same manner as in Example 1 except that 2 parts of Riken Vitamin Co., Ltd. was used.

Example 4 The preparation of a room temperature curable composition was carried out in the same manner as in Example 3 except that the content of “Riquemar S-71-D” was 5 parts based on 100 parts of “MS polymer S203”. Thus, a room temperature curable composition was obtained.

Example 5 In the preparation of a room temperature curable composition, diglycerin monostearate (trade name) was used as a fatty acid ester instead of “Riquemar S-71-D” for 100 parts of “MS polymer S203”. A room temperature-curable composition was obtained in the same manner as in Example 3, except that 2 parts of “Liquemar DS-100A” manufactured by Riken Vitamin Co., Ltd.) was used.

Example 6 A room temperature-curable composition was prepared in the same manner as in Example 5 except that the content of “Riquemar DS-100A” was changed to 5 parts with respect to 100 parts of “MS polymer S203”. A curable composition was obtained.

(Example 7) In the preparation of a room temperature curable composition, sorbitan stearate (trade name “Liquemar S-L”) was used as a nonionic surfactant in place of the amine compound for 100 parts of “MS polymer S203”. 300
W ", manufactured by Riken Vitamin Co., Ltd.), and a room temperature-curable composition was obtained in the same manner as in Example 1 except that 2 parts were used.

(Example 8) A room temperature curable composition was prepared in the same manner as in Example 7, except that the content of "Riquemar S-300W" was changed to 5 parts with respect to 100 parts of "MS polymer S203". A curable composition was obtained.

Example 9 In the preparation of a room temperature curable composition, glycerin monostearate (commercially available) was used as a nonionic surfactant in place of “Likemar S-300W” per 100 parts of “MS polymer S203”. A room temperature curable composition was obtained in the same manner as in Example 7, except that 2 parts of the name “Riquemar S-100” manufactured by Riken Vitamin Co., Ltd. was used.

(Comparative Example 1) In the preparation of a room temperature curable composition, 100 parts of “MS polymer S203” was added to CH
Room temperature curable composition in the same manner as in Example 1 except that 2 parts of CH ₃ (CH ₂ ) ₁₇ NH ₂ was added as an amine compound instead of ₃ (CH ₂ ) ₁₇ NH (CH ₂ ) ₃ NH ₂ . I got

(Comparative Example 2) In the preparation of the room-temperature curable composition, Example 1, Example 3, or Example 1 was repeated except that none of the amine compound, fatty acid ester and nonionic surfactant was contained. A room temperature curable composition was obtained in the same manner as in Example 7.

The performances of the nine room temperature curable compositions obtained in Examples 2 to 9 and Comparative Examples 1 and 2 were evaluated in the same manner as in Example 1. The results were as shown in Table 2.

[0080]

[Table 2]

As is clear from Table 2, the room-temperature curable compositions of Examples 1 to 9 according to the present invention almost always cause contamination on the surface of the cured product even after 3 months of outdoor exposure at a 30 ° angle on the south side. And the elongation of the cured product was excellent.

On the other hand, the room-temperature curable composition of Comparative Example 1 containing a monoamine as an amine compound had a
After three months of outdoor exposure at a 0 degree angle, considerable contamination was observed on the surface of the cured product, and the elongation rate of the cured product was slightly inferior.

The room-temperature curable composition of Comparative Example 2, which contained neither an amine compound nor a fatty acid ester or a nonionic surfactant, showed severe contamination on the surface of the cured product after three months of outdoor exposure at a 30 ° angle on the south side. Was observed, and the elongation percentage of the cured product was slightly inferior.

Example 10 Polyether-based polymer (trade name “MS Polymer S-203” manufactured by Kaneka Chemical Industry Co., Ltd.) 1
2 parts by weight of sorbitan sterate and a glass balloon (trade name “CELLSTAR Z” manufactured by Asahi Glass Co., Ltd.)
27 ") 10 parts by weight, 100 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, and 60 parts by weight of polypropylene glycol were added, uniformly mixed with a closed stirrer, and heated under reduced pressure at 110 ° C. for 2 hours. After the mixture was dehydrated and cooled to 30 ° C., 3 parts by weight of vinylmethoxysilane, 2 parts by weight of aminomethylaminopropyltrimethoxysilane, and 2 parts by weight of dibutyltin dilaurate were uniformly dispersed in the mixture. The obtained mixture was molded and cured into a sheet having a thickness of 3 mm, and the physical properties were evaluated. Evaluation of Physical Properties Evaluation of Glossiness The 60 ° specular gloss was measured according to JIS Z8741.

Example 11 Sorbitan sterate was added to 5
A room temperature curable composition was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 12 A room temperature curable composition was prepared in the same manner as in Example 1 except that glycerin monostearate was added in an amount of 2 parts by weight instead of sorbitan stearate.

Example 13 A room temperature curable composition was prepared in the same manner as in Example 1 except that the amount of the glass balloon was changed to 15 parts by weight.

Comparative Example 3 A room temperature curable composition was prepared in the same manner as in Example 1 except that sorbitan sterate was not added.

Comparative Example 4 A room temperature curable composition was prepared in the same manner as in Example 1 except that no glass balloon was added. Table 3 shows the blending ratios of the room-temperature curable compositions and the results of evaluation of the physical properties prepared in Examples 10 to 13 and Comparative Examples 3 and 4.

[0090]

[Table 3]

As is evident from Table 3, the curable compositions at room temperature of Examples 8 to 12 according to the present invention almost always cause contamination on the surface of the cured product even after 3 months of outdoor exposure at a 30 degree angle on the south side. And the elongation and gloss of the cured product were excellent.

On the other hand, the room-temperature-curable compositions of Comparative Examples 3 and 4, which did not contain a glass balloon, had extremely poor glossiness.

Reference Example Synthesis of (meth) acrylate Polymer An alkyl (meth) acrylate copolymer corresponding to the (meth) acrylate polymer was synthesized according to the following method. A 2-liter separable flask equipped with a thermometer, a cooling tube, and a dropping funnel was charged with 200 g of toluene, stirred while purging with nitrogen, heated to 80 ° C. by an oil bath, and then 2 g of azobiscyclohexanecarbonitrile was added with toluene. A solution dissolved in 10 g is added and then n-butyl acrylate 150
g, 330 g of methyl methacrylate, 20 g of 3-methacryloxypropyltrimethoxysilane, and 25 g of 3-mercaptopropyltrimethoxysilane were added dropwise over 2 hours to carry out polymerization. Three hours after the completion of the dropwise addition, a solution prepared by dissolving 2 g of azobiscyclohexanecarbonitrile in 10 g of toluene was added again, and the mixture was heated and stirred for 2 hours to carry out polymerization. A solution of an acrylic copolymer having a silyl group was obtained. The obtained crosslinkable acrylic copolymer having a hydrolyzable silyl group had a number average molecular weight of 5,300 and a weight average molecular weight of 9,900 as determined by gel permeation chromatography (GPC) in terms of styrene.
Met.

(Example 14) Polyether-based polymer (trade name “MS Polymer S-203” manufactured by Kaneka Corporation) 8
0 parts by weight and (meth) acrylate copolymer 20
Parts by weight, 2 parts by weight of sorbitan sterate, 100 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, and 60 parts by weight of polypropylene glycol are mixed uniformly with a closed stirrer, and the pressure is reduced at 110 ° C. for 2 hours. After heating to dehydrate the mixture, the mixture was cooled to 30 ° C., and then 3 parts by weight of vinylmethoxysilane, 2 parts by weight of aminomethylaminopropyltrimethoxysilane, and 2 parts by weight of dibutyltin dilaurate were uniformly mixed with the mixture. Dispersed. The obtained mixture was molded and cured into a sheet having a thickness of 3 mm, and the physical properties were evaluated.

(Example 15) Sorbitan sterate was added to 5
A room temperature curable composition was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 16 A room temperature curable composition was prepared in the same manner as in Example 1 except that glycerin monostearate was added in an amount of 2 parts by weight in place of sorbitan sterate.

Comparative Example 5 A room temperature curable composition was prepared in the same manner as in Example 1 except that sorbitan sterate was not added.

Comparative Example 6 A room temperature curable composition was prepared in the same manner as in Example 1 except that the (meth) acrylate polymer was not added.

Comparative Example 7 A room temperature curable composition was prepared in the same manner as in Example 1 except that sorbitan sterate was used in an amount of 5 parts by weight and a (meth) acrylate polymer was not added.

Comparative Example 8 Curing at room temperature was performed in the same manner as in Example 1 except that 2 parts by weight of glycerin monostearate was added instead of sorbitan sterate, and no (meth) acrylate polymer was added. The composition was prepared. Table 4 shows the mixing ratios of the room-temperature-curable compositions prepared in Examples 14 to 16 and Comparative Examples 5 to 8 and the evaluation results of physical properties.

[0101]

[Table 4]

As is evident from Table 4, the room-temperature curable compositions of Examples 14 to 16 according to the present invention hardly cause contamination on the surface of the cured product even after 3 months of outdoor exposure at a 30 degree angle on the south side. And the elongation of the cured product was excellent.

On the other hand, the room-temperature curable compositions of Comparative Examples 5 to 8, which did not contain the (meth) acrylic acid ester-based polymer, had a cured product surface durability after 3 months of outdoor exposure at a 30 ° angle on the south side. Was inferior.

[0104]

As described above, the room-temperature-curable composition according to any one of claims 1 to 4 hardly causes contamination with time on the surface of the cured product without using a surface protective agent, and Since it exhibits excellent physical properties after curing, it is suitably used as a sealing material or an adhesive for various applications.
According to the room-temperature-curable composition of claim 5, it is possible to obtain a moderately glossy state (a state in which so-called "tekari" does not appear) without applying a matte paint, and does not give a sense of inexpensiveness. An adhesive can be obtained.

Claims (5)

[Claims] 1. The main chain is essentially a polyether,
At least one terminal has a crosslinkable hydrolyzable silyl group and has a number average molecular weight of 4,000 to 30,000 per 100 parts by weight of a polyether-based polymer.
A room temperature curable composition comprising 0.1 to 20 parts by weight of an amine compound having at least two amino groups and having a melting point of 10 to 200 ° C, and a silanol condensation catalyst. 2. The method according to claim 1, wherein the main chain is essentially a polyether,
At least one terminal has a crosslinkable hydrolyzable silyl group, and the number-average molecular weight is 4,000 to 30,000 based on 100 parts by weight of the polyether-based polymer, the degree of polymerization is 2
Fatty acid ester of polyglycerin which is 5 0.1-20
A room temperature curable composition comprising parts by weight and a silanol condensation catalyst. 3. The backbone is essentially a polyether,
It has a crosslinkable hydrolyzable silyl group at at least one terminal, and has a melting point of 10 to 100 parts by weight of a polyether polymer having a number average molecular weight of 4000 to 30,000.
A room temperature curable composition comprising 0.1 to 20 parts by weight of a nonionic surfactant at 200 ° C and a silanol condensation catalyst. 4. The backbone is essentially a polyether,
A polyether polymer having a crosslinkable hydrolyzable silyl group at at least one terminal and having a number average molecular weight of 4,000 to 30,000, and a (meth) acrylate copolymer having a main chain of essentially a (meth) acrylate ester Has at least one crosslinkable hydrolyzable silyl group and has a number average molecular weight of 60
The melting point is 10 to 100 parts by weight in total with the (meth) acrylate-based polymer of 100 to 30,000.
A room temperature curable composition comprising 0.1 to 20 parts by weight of a nonionic surfactant at 200 ° C and a silanol condensation catalyst. 5. The method of claim 1, wherein the backbone is essentially a polyether,
It has a crosslinkable hydrolyzable silyl group at at least one terminal, and has a melting point of 10 to 100 parts by weight of a polyether polymer having a number average molecular weight of 4000 to 30,000.
A room temperature curable composition comprising 0.1 to 20 parts by weight of a nonionic surfactant at 200 ° C., 2 to 30 parts by weight of a filler having an average particle size of 10 to 80 μm, and a silanol condensation catalyst. Stuff.