JP2001288374A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition having resolved problems in weatherability, water resistance, surface staining, etc., each involved in conventional curable compositions using crosslinkable silyl group-containing organic polymer. SOLUTION: This curable composition is obtained by combining the above- mentioned organic polymer with a hydroxy group-containing acrylic polymer and/or hydroxy group-containing methacrylic polymer 500-100,000 in average molecular weight. Thus, above-mentioned problems have been solved and this curable composition can be applicable to a wide range of uses including sealants, adhesives and coatings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition and, more particularly, to an excellent cured rubber-like elastic material which is cured by moisture in the atmosphere and has high weather resistance and water resistance. In addition, the plasticizer contained does not migrate to the surface, nor does it migrate to the surface of the overcoated paint, so the surface is not sticky and there is no dust adhesion contamination, such as sealing materials, adhesives, paints, etc. And an excellent cured composition having a wide range.

[0002]

2. Description of the Related Art Crosslinkable silyl group-containing organic polymers are used in various fields such as sealing materials for construction, civil engineering, automobiles, adhesives, and paints because of their good rubber elasticity and workability. I have. When used for sealing materials and paints, high weather resistance and water resistance are required from the point of maintaining performance and aesthetics, and there is no surface contamination due to dust adhesion. For maintenance, performance such as high water resistance is required. When used in such applications, in order to adjust the viscosity and physical properties, for example, it is common to add a low molecular weight plasticizer such as dioctyl phthalate, but weather resistance and water resistance are reduced There is a disadvantage that it will. In addition, these plasticizers migrate to the surface of the cured product, or when the paint is further applied to the surface of the cured product, the plasticizer migrates to the surface of the paint, making the surface sticky and adhering dust. There is the disadvantage that contamination occurs.

[0003] In order to remedy these drawbacks, methods using various polymeric plasticizers have been proposed. For example, JP-A-63-108058 and JP-A-02-1428
In the publication No. 50 or the like, a molecular weight of 100 to 8 is used as a plasticizer.
000 polyalkylene ether polyol or a polyoxyalkylene monoether having a molecular weight of 500 to 5,000 prevents the plasticizer from migrating to the surface of the cured product or to the paint overcoated on the cured product, and surface contamination due to dust adhesion And the like are disclosed. However, the above-described method has problems in that the effect of preventing surface contamination is not sufficient, and that the weather resistance and the water resistance are reduced.

[0004] The present invention solves the above-mentioned drawbacks of the prior art, and becomes a rubber-like elastic body having high weather resistance and water resistance by being cured by moisture in the air or the like. A useful cured composition with a wide range of applications, such as sealing materials, adhesives, and paints, that prevents the plasticizer from migrating to the surface of the cured product or to the paint overcoated on the cured product, and prevents surface contamination due to dust adhesion. The purpose is to provide.

[0005]

Means for Solving the Problems To achieve the above object, as a result of intensive studies, they have found that the above problem can be solved by using a specific polymer plasticizer,
The present invention has been reached. That is, the present invention relates to the invention described below. 1. (A) a crosslinkable silyl group-containing organic polymer and (B)
A curable composition comprising a hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer having an average molecular weight of 500 to 100,000.

[0006] 2. In the curable composition, the amount of the hydroxyl group-containing acrylic polymer and / or the hydroxyl group-containing methacrylic polymer having an average molecular weight of the component (B) of 500 to 100,000 is such that the crosslinkable silyl group-containing organic polymer of the component (A) is used. A curable composition characterized in that the amount is 1 to 200 parts by weight based on 100 parts by weight of the united product. 3. The curable composition according to claim 1 or 2, wherein the curable composition further contains (C) a crosslinking catalyst, and (D) an antioxidant and / or an ultraviolet absorber. .

[0007] 4. 4. The curable composition according to the above item 3, wherein the curable composition further contains (E) an additive. 5. 5. The method according to any one of the above items 1 to 4, wherein the component (A) is a crosslinkable silyl group-containing polyoxyalkylene polymer and / or a crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer. The curable composition according to item.

[0008] 6. The crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer described above is a crosslinkable silyl group-containing acryl-modified polyoxyalkylene polymer, and / or
Or a crosslinkable silyl group-containing organic polymer selected from one or more of a crosslinkable silyl group-containing methacryl-modified polyoxyalkylene polymer; . 7. The above-mentioned component (B) is obtained by a high-temperature continuous polymerization reaction of a vinyl monomer in the presence or absence of a polymerization initiator, and has an average molecular weight of 500 to 100,000, Tg of 0 ° C or less, 25 ° C. A hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer having a viscosity of 100,000 mPa · s or less.
Item 6. Each curable composition according to any one of items 5 to 5. 8. Further, the present invention relates to the curable composition according to any one of the above items 1 to 6, wherein the curable composition is any of a sealing material, an adhesive, and / or a paint. .

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The crosslinkable silyl group-containing organic polymer (A) in the present invention has one silyl group in the molecule which forms a siloxane bond by the action of moisture in the air or the like to form a rubber-like elastic cured product. Any organic polymer containing the above can be used as long as it is such a material. In addition, not only one kind but also two kinds of this crosslinkable silyl group-containing organic polymer can be used. A blend of the above can also be used.

Examples of the organic polymer in such a crosslinkable silyl group-containing organic polymer include a polyoxyalkylene polymer or copolymer, a vinyl-modified polymer thereof,
Examples include vinyl-based polymers or copolymers such as polyacryl polymers, polymethacryl polymers, and polyolefins, polyesters, and mixtures thereof. These are described in, for example, JP-A-52-73998, JP-A-54-6097, JP-A-59-78223, JP-A-59-122541, JP-A-60-6747, and JP-A-60-6747. No. 61-233043, JP-A-61-241319
JP-A-63-112642, JP-A-02-432
03, JP-A-04-283259, JP-A-05-7
0531, JP-A-05-287186 and JP-A-06-186
These are described in, for example, Japanese Patent Application Laid-Open No. 172631, Japanese Patent Application Laid-Open No. H11-80571, and Japanese Patent Application Laid-Open No. H11-116763, and are already known. Hereinafter, in this specification, acrylic monomers and polymers, methacrylic monomers and polymers such as methacrylic monomers and polymers are collectively referred to as (meth) acrylic…,
For example, it may be referred to as a (meth) acrylic polymer.

The crosslinkable silyl group bonded to these polymers has one to one in the molecule in view of curability and physical properties after curing.
Preferably, five are included. Various types of crosslinkable silyl groups are known, and among them, the one represented by the following general formula 1 which is easily crosslinked and easily produced is preferable.

[0012]

Embedded image

(Wherein, R represents a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms,
Of these, a methyl group is most preferred. X is a halogen atom,
A reactive group selected from a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group; May be the same group or different groups.
X is preferably an alkoxy group, more preferably a methoxy group. a is an integer of 0, 1 or 2, and 1 is preferred. )

Examples of the polyoxyalkylene polymer include polyoxyalkylene polymers and copolymers, such as polyoxyethylene polymers, polyoxypropylene polymers, polyoxybutylene polymers, polyoxytetramethylene polymers, and polyoxyalkylene polymers and copolymers. And block copolymers of the formula (1).

These polyoxyalkylene polymers may be further modified with vinyl, and the vinyl monomer for modifying vinyl has at least one polymerizable double bond in the molecule. Compounds, such as unsaturated monocarboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, etc.) and unsaturated monocarboxylic acid esters (eg, methyl of unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, etc.) Esters of ethyl, propyl, butyl, 2-ethylhexyl or benzyl), unsaturated polycarboxylic acids or esters thereof (for example, maleic anhydride, maleic acid, mono- and dialkyl esters of maleic acid, etc.), Saturated compounds (for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate) Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, etc., epoxy group-containing unsaturated compounds (eg, glycidyl acrylate, glycidyl methacrylate, etc.), nitrile group-containing unsaturated Compounds (eg, acrylonitrile, methacrylonitrile, etc.), amino group-containing unsaturated compounds (eg, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc.), amide group-containing unsaturated compounds (eg, acrylamide, meta Acrylamide), aliphatic vinyl monomers (eg, ethylene, propylene, isobutylene, etc.), and aromatic hydrocarbon vinyl monomers. (Eg, styrene, α-methylstyrene, etc.), dienes (eg, butadiene, isoprene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. No.

The amount of the vinyl monomer to be vinyl-modified is preferably 0.1 to 1000 parts by mass, more preferably 1 to 200 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer.

Examples of the vinyl polymer include an acrylate polymer or copolymer, a methacrylate polymer or copolymer, a polyolefin polymer or a copolymer, and an acrylate polymer or copolymer. As the polymer, methyl acrylate polymer, ethyl acrylate polymer, 2-ethylhexyl acrylate polymer, etc., and as the methacrylate polymer or copolymer, methyl methacrylate polymer, ethyl methacrylate polymer, etc. Examples of the polyolefin polymer or copolymer include polyisobutylene, polybutadiene, hydrogenated polybutadiene, polyisobrene, and copolymers thereof.

Examples of the polyester polymer include polyethylene adipate, polypropylene adipate, polybutylene adipate, polyethylene phthalate, and a copolymer thereof.

Examples of the crosslinkable silyl group-containing organic polymer include:
From the viewpoint of adhesion after curing, elastic properties, etc., a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer is preferable,
Among these, a crosslinkable silyl group-containing polyoxypropylene polymer, a crosslinkable silyl group-containing acryl-modified polyoxypropylene polymer or a crosslinkable silyl group-containing methacryl-modified polyoxypropylene polymer is more preferable. Further, the use of the crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer has an effect of further increasing the weather resistance of the cured composition.

The above-mentioned vinyl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule is
For example, a method in which one or more vinyl monomers are polymerized by a usual known radical polymerization method in the presence of a crosslinkable silyl group-containing polyoxyalkylene polymer (for example, Kaisho 59-78
No. 223, Japanese Patent Publication No. 02-42367),
Alternatively, a method of blending a crosslinkable silyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing vinyl polymer (for example, JP-A-06-172631)
However, the present invention is not limited to these methods.

A method for introducing a crosslinkable silyl group into an organic polymer can be carried out by a known method. For example, a method in which the terminal of an organic polymer is allylated with olefin and a hydrosilane compound such as methyldimethoxysilane is added thereto. ,
When synthesizing an organic polymer by polymerizing vinyl monomers,
A method of copolymerizing a compound containing a vinyl group and a crosslinkable silyl group in a molecule such as vinylmethyldimethoxysilane, or introducing an active hydrogen group such as a hydroxyl group into an organic polymer, and γ-isocyanatopropyltriethoxysilane or the like. Examples of the method include a method in which a compound having an isocyanate group and a crosslinkable silyl group in the molecule is reacted, but the method is not limited thereto.

In the present invention, the crosslinkable silyl group-containing organic polymer has a molecular weight of 1,000 or more, especially 6,000.
Those having a molecular weight distribution in the range of from 30,000 to 30,000 and having a narrow molecular weight distribution are easy to handle because of low viscosity before curing, and have extremely excellent elastic properties such as strength, elongation and modulus after curing and physical properties such as adhesion.

The (B) hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer used in the present invention adjusts the viscosity of the composition before curing the composition and improves workability such as coating. After the composition is cured, it adjusts the elastic properties such as strength, elongation, and modulus of the cured product, 2 increases the weather resistance and water resistance, and 3 overcoats the surface of the cured product or the cured product. Therefore, the surface does not become sticky, and as a result, there is an effect that contamination due to adhesion of dust is prevented.

The hydroxyl group-containing (meth) acrylic polymer of the component (B) comprises (i) a hydroxyl group-containing acrylic monomer and / or a hydroxyl group-containing methacrylic monomer.
i) A copolymer with a vinyl monomer other than the above (i), wherein a small amount of the component (i) is used when one or more of the vinyl monomers of the component (ii) are polymerized. Is a copolymer component having a narrow molecular weight distribution obtained by continuously polymerizing at 180 to 300 ° C. in the presence or absence of a radical polymerization initiator.

The hydroxyl group-containing acrylic monomer or the hydroxyl group-containing methacrylic monomer of the component (i) includes:
Examples thereof include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and hydroxypropyl methacrylate.

The vinyl monomer of the component (ii) is a compound having one or more polymerizable double bonds in the molecule and includes, for example, unsaturated monocarboxylic acids (for example, acrylic acid, Acrylic acid, itaconic acid, etc.),
Unsaturated monocarboxylic acid esters (eg, methyl, ethyl, propyl, butyl, 2-ethylhexyl of unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid);
Or esters such as benzyl), unsaturated polycarboxylic acids or esters thereof (eg, maleic anhydride,
Maleic acid, mono- and dialkyl esters of maleic acid, etc., unsaturated compounds containing epoxy groups (for example,
Glycidyl acrylate, glycidyl methacrylate, etc.), nitrile group-containing unsaturated compounds (eg, acrylonitrile, methacrylonitrile, etc.), amino group-containing unsaturated compounds (eg, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc.) Amide group-containing unsaturated compounds (eg, acrylamide, methacrylamide, etc.), aliphatic vinyl monomers (eg,
Ethylene, propylene, isobutylene, etc.), aromatic hydrocarbon-based vinyl monomers (eg, styrene, α-methylstyrene, etc.), dienes (eg, butadiene,
And vinyl esters (such as vinyl acetate and vinyl propionate), vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

Preferred among the vinyl monomers of component (ii) are unsaturated monocarboxylic esters, more preferably alkyl (meth) acrylates, such as methyl acrylate, Examples thereof include methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. In addition, these (meta)
The vinyl monomer of the third component that can be used together with the alkyl acrylates is a vinyl aromatic monomer represented by styrene.

The component (B) has an average molecular weight of 500 to 500.
100,000, preferably 1000-5000
0, more preferably 7000 to 30,000. 50
If it is less than 0, migration to the cured product surface occurs, and
If it exceeds 3, the viscosity and Tg increase, and the workability of the cured composition deteriorates. The Tg of the component (B) is preferably 0 ° C. or lower, more preferably -10 ° C. or lower. If the temperature is higher than 0 ° C., the ability to control the physical properties of the cured composition and the workability at a low temperature are deteriorated. The viscosity of the component (B) is
At 25 ° C., the pressure is preferably 100000 mPa · s or less, more preferably 50,000 mPa · s or less. 1000
If it exceeds 00 mPa · s, the workability of the cured composition will be poor. The component (B) is used in an amount of 1 to 200 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer in order to adjust the workability of the cured composition and the physical properties after curing. It is preferred to use 100 parts by weight.

As described above, as the hydroxyl group-containing (meth) acrylic polymer of the component (B), the hydroxyl group-containing (meth) acrylic monomer and the hydroxyl group-containing (meth) acrylic monomer are further required in the main component of the alkyl (meth) acrylate. Those obtained by copolymerizing a vinyl aromatic monomer such as styrene accordingly are preferred.

The cross-linking catalyst (C) in the present invention is a catalyst for cross-linking (curing) the crosslinkable silyl group-containing organic polymer, and specifically includes, for example, stannas octoate, dibutyltin dioctoate Organic such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin phthalate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin dimaleate, dioctyltin divertate Tin compounds; titanates such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; phosphoric acid, monobutyl phosphate, monooctyl Acidic compounds such as p-toluenesulfonic acid; phosphate, dibutyl phosphate, phosphoric acid or phosphoric acid esters such as dioctyl phosphate;
Examples include amines such as cyclohexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, dodecylamine, and triethanolamine. These can be used alone or in combination of two or more. Of these, dibutyltin diacetylacetonate is preferred because of its high crosslinking rate, toxicity and relatively low volatility. Component (C) comprises a crosslinking rate,
From the viewpoint of the physical properties of the cured product, it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer.

In the present invention, (D) an antioxidant and / or
Alternatively, an ultraviolet absorber is used to prevent oxidation and light deterioration of a cured product and increase weather resistance. Specifically, a hindered amine-based or hindered phenol-based antioxidant, benzotriazole System, triazine system,
Examples include benzophenone-based and benzoate-based ultraviolet absorbers, and one or two or more selected from these are used. Examples of the above-mentioned various antioxidants and ultraviolet absorbers include Polymer Additive Product Catalog (199) of Ciba Specialty Chemicals Co., Ltd.
Ninth Edition) or Sanol Co., Ltd.'s catalog of Stanols for Polymers (1991 Edition). Typical examples include those described below, but are not limited thereto. It is not something to be done.

Hindered amine antioxidants include:
For example, N, N ', N ", N"'-tetrakis- (4,
6-bis- (butyl- (N-methyl-2,2,6,6-
Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-
Diamine, dibutylamine-1,3,5-triazine-
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl-1,6-hexamethylenediamine / N-
Polycondensate of (2,2,6,6-tetramethyl-4-piperidyl) butylamine, 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}],
Dimethyl succinate and 4-hydroxy-2,2,6,6-
High molecular weight type such as a polymer of tetramethyl 1-piperidine ethanol, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4] -Hydroxyphenyl] methyl] butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,
Low molecular weight types such as a mixture of 2,2,6,6-pentamethyl-4-piperidyl sebacate and the like can be mentioned.

Examples of hindered phenolic antioxidants include, for example, pentaerythritol tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]. Examples of the ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2H-benzotriazole-
Benzotriazole-based ultraviolet absorbers such as 2-yl) -4,6-di-tert-pentylphenol, 2- (4,6-
Diphenyl-1,3,5-triazin-2-yl) -5
A triazine-based ultraviolet absorber such as-[(hexyl) oxy] -phenol, a benzophenone-based ultraviolet absorber such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy Examples include benzoate-based ultraviolet absorbers such as benzoate.

Component (D) is used in an amount of 0.1 to 10 parts by weight, especially 0.5 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer in order to enhance the weather resistance of the cured product. It is preferable to use parts.

Further, the (E) additive used in the present invention means (D) an additive other than an antioxidant and / or an ultraviolet absorber, and specifically, a coupling agent, a filler, Additives such as thixotropic agents, storage stability improvers, and colorants. Of these, coupling agents, thixotropic agents and / or
Or the filler improves adhesion, increases the amount of base polymer,
It is preferable to use them together for reinforcement and to prevent drooping.

Examples of the coupling agent include silane-based, aluminum-based, and zirco-aluminate-based coupling agents. Among them, silane-based coupling agents are preferable because of their excellent adhesiveness. As this silane coupling agent, specifically, N- (2-aminoethyl) 3
-Aminopropylmethyldimethoxysilane, N- (2-
Examples thereof include compounds having a molecular weight of 500 or less, preferably 400 or less, containing an alkoxysilyl group, such as (aminoethyl) 3-aminopropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.

Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, and organic thixotropic agents such as organic bentonite, modified polyester polyols and fatty acid amides. Calcium and the like can be mentioned, and among them, fatty acid amide and fatty acid-treated calcium carbonate are preferable.

As the filler, powdery fillers such as calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, clay, kaolin, talc, calcium silicate, diatomaceous earth, and carbon black;
Flaky fillers such as mica; fibrous fillers such as whiskers and glass fibers;
μm is preferred, of which calcium carbonate is preferred. These fillers can be used alone or in combination of two or more.

Examples of the storage stability improver include compounds which react with water contained in the composition and include low molecular weight crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, and calcium oxide.

Examples of the coloring agent include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

The amount of the component (E) additive may be appropriately determined according to the type of the additive and the purpose of use. For example, the filler is used in an amount of 0 to 800 parts by weight, preferably 50 to 400 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. Here, a composition of a sealing material is shown as one example of the cured composition, but is not limited thereto.

Example 1 In a kneading vessel equipped with a heating device, an acrylic-modified polyoxypropylene polymer containing a crosslinkable silyl group) (MS polymer MS)
X911, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) 200 g, hydroxyl group-containing acrylic polymer (ARUFON UH-2000, molecular weight 13,000, Tg = -55 ° C., viscosity 10,000 to 2)
0000 mPa · s / 25 ° C., OH value = 20 mg KOH /
g, manufactured by Toagosei Co., Ltd.), 130 g, hindered phenolic antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals, Inc.), 4 g, fatty acid-treated calcium carbonate (Calfine 200M, Maruo Calcium Co., Ltd.)
250 g), 9 g of fatty acid amide (fatty acid amide S, manufactured by Kao Corporation), and 10 g of vinyltrimethoxysilane (Sila Ace S210, manufactured by Chisso Corporation) are stirred and mixed until the contents become uniform. , Dispersed. Thereafter, dehydration under reduced pressure was performed at 110 ° C. for 1 hour, and after cooling, 2 g of dibutyltin diacetylacetonate (Neostan U-220, manufactured by Nitto Kasei Co., Ltd.), N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane (Silaace) S
310, manufactured by Chisso Corporation), and the mixture was stirred and mixed to prepare a sealing material composition.

Example 2 In Example 1, 200 g of a crosslinkable silyl group-containing polyoxypropylene polymer (ES-S3630, manufactured by Asahi Glass Co., Ltd.) was used instead of the crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer. A sealing material composition was prepared in the same manner except that the above procedure was performed.

Comparative Example 1 In Example 1, polyoxypropylene glycol (PPG Di) was used instead of the hydroxyl group-containing acrylic polymer.
ol-3000, manufactured by Mitsui Chemicals, Inc.) in the same manner except that 130 g of a sealing material composition was prepared.

Comparative Example 2 In Example 2, polyoxypropylene glycol (PPG Di) was used instead of the hydroxyl group-containing acrylic polymer.
ol-3000, manufactured by Mitsui Chemicals, Inc.) was used in the same manner except that 130 g of a sealing material composition was prepared.

Table 1 shows the data of these examples and comparative examples.

[Table 1]

Each data in Table 1 is based on the following measurement test. [Performance Test] (1) Weather Resistance The obtained sealing material composition was cured into a sheet to prepare a sheet having a thickness of 5 mm. This sheet, JIS
K6266: Using a sunshine weatherometer according to 1996, the state of the surface of the cured sealing material after irradiation for 500 hours, 1000 hours, 2000 hours, and 3000 hours was visually observed to determine weather resistance. Judgment criteria: 〇: No hair cracks on the surface of the sealing material ×: Many hair cracks on the surface of the sealing material (2) Extrudability JIS A1439: 1997 “Extrusion with a 4.14 test cartridge” in “Testing methods for building sealing materials” Test (measuring temperature 23 ° C.).

(3) Slump Slump (longitudinal) was measured (measuring temperature 23 ° C.) according to “4.1 Slump test” of JIS A1439: 1997 “Testing method for building sealing material”. (4) Tensile adhesion (after curing) A test was conducted in accordance with JIS A1439: 1997 "4.21 Tensile adhesion test" of "Testing method for building sealing materials" (measuring temperature 23 ° C). The test piece was prepared by using a slate as a primer (OP2531, manufactured by Auto Chemical Industry Co., Ltd.).
At 23 ° C. and 50 ° C.
% Relative humidity for 14 days, then cured at 30 ° C. for 14 days.

(5) Modulus As a result of the tensile adhesion test after curing, the one having a 50% tensile stress (M50) of 22 N / cm ² or less was evaluated as Δ. (6) Tensile adhesion (after immersion in water) In accordance with JIS A1439: 1997 "Test method for building sealing materials", "4.21 Tensile adhesion test",
After the cured specimen was placed in 23 ° C. water for 7 days,
A tensile test was immediately performed (measuring temperature 23 ° C.).

(7) Contamination to topcoat paint (50 ° C.
Acceleration conditions) Use a slate plate with a thickness of 5 mm, depth 5 mm, width 25
mm, a joint having a length of 200 mm was prepared, a sealing material composition was poured into the joint, an excess sealing material was scraped off with a spatula, and the surface was flattened at 23 ° C. and 50% relative humidity for 24 hours. Cured. Next, a water-based acrylic paint (Tile rack water-based top super white, manufactured by Nippon Paint Co., Ltd.) was applied to the surface of the cured sealing material, and cured at the above temperature and humidity for another 7 days. After the cured specimen is placed in a 50 ° C. thermostat and heat-treated for 10 days,
The test piece was taken out of the thermostat and sprinkled with black silica sand (particle diameter: 70 to 110 μm) on the surface of the overcoated paint. The test piece was immediately turned over, and the bottom was patted lightly by hand to drop excess black silica sand. The state of black silica sand (dirt) remaining on the surface was visually observed to determine the contamination. Judgment criteria 〇: The surface of the paint overcoated with the sealing material is clean without adhesion of black silica sand ×: The black silica sand is adhered to the surface of the paint overcoated with the sealing material and is black and dirty

[Effect of the Invention] As described above, the cured composition of the present invention becomes a rubber-like elastic body having high weather resistance and water resistance when cured by moisture such as in the air.
In order to prevent the plasticizer from migrating to the surface of the cured product or to the paint applied to the cured product, and to prevent surface contamination due to dust adhesion, high weather resistance, high water resistance and contamination prevention due to dust adhesion are required. It has become possible to provide a particularly useful cured composition for sealing materials, adhesives, paints and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/00 C08L 71/00 A C09D 133/14 C09D 133/14 171/00 171/00 201/10 201 / 10 C09J 133/14 C09J 133/14 171/00 171/00 201/10 201/10 (72) Inventor Takanori Onoda 2044 No. 6, Kami Inakichi, Chiyoda-cho, Shinji-gun, Ibaraki Pref. 72) Inventor Osamu Takeda 2044-6, Kamiinakichi, Chiyoda-cho, Niigata-gun, Ibaraki F-Term in the Technical Research Laboratory of Auto Chemical Industry Co., Ltd. EC076 EE027 EJ067 EN026 EN106 EP018 EP027 EU087 EU177 EU187 EV236 EW046 EX078 EZ036 EZ046 FB238 FD057 FD077 FD098 GH01 GJ01 GJ02 4J038 CG141 CG142 CH121 CH12 2 CL001 CL002 GA02 GA03 GA09 GA12 GA13 GA15 HA026 HA206 HA216 HA416 HA446 HA456 HA466 HA486 HA536 HA546 JA33 JA65 JB02 JB09 JB35 JB36 JC13 JC22 JC24 JC40 KA03 KA04 KA08 LA06 MA14 NA03 NA04 NA05 NA10 NA11 PA20 PB05 DM04 4 GA03 GA04 GA05 GA22 GA24 GA29 HA036 HA156 HA166 HA196 HA286 HA306 HA316 HA356 HB37 HB38 HC03 HC04 HC08 HC11 HC25 HD13 HD24 HD33 HD41 HD43 JB03 KA16 KA27 KA29 KA30 KA35 LA07 MA04 NA12

Claims (8)

[Claims] 1. A curable composition comprising (A) a crosslinkable silyl group-containing organic polymer and (B) a hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer having an average molecular weight of 500 to 100,000. 2. The curable composition according to claim 1, wherein the amount of the component (B) used is 1 to 200 parts by weight per 100 parts by weight of the component (A). Item 10. The curable composition according to Item 1. 3. The curable composition further comprises (C)
The curable composition according to claim 1, further comprising a crosslinking catalyst, and (D) an antioxidant and / or an ultraviolet absorber. 4. The curable composition according to claim 1, further comprising (E)
The curable composition according to claim 3, further comprising an additive. 5. The composition according to claim 1, wherein said component (A) is a crosslinkable silyl group-containing polyoxyalkylene polymer and / or a crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer. 5. The curable composition according to any one of 4. 6. The crosslinkable silyl group-containing vinyl-modified polyoxyalkylene polymer is a crosslinkable silyl group-containing acryl-modified polyoxyalkylene polymer and / or a crosslinkable silyl group-containing methacryl-modified polyoxyalkylene polymer. 6. A crosslinkable silyl group-containing organic polymer selected from one or two or more kinds of coalescing.
The curable composition according to item. 7. The component (B) is obtained by a high-temperature continuous polymerization reaction of a vinyl monomer in the presence or absence of a polymerization initiator, and has an average molecular weight of 500 to 100,000 and a Tg of 0 ° C. or lower. , Viscosity at 25 ° C. is 100,000 mPa · s
The curable composition according to any one of claims 1 to 6, wherein the curable composition is the following hydroxyl-containing acrylic polymer and / or hydroxyl-containing methacrylic polymer. 8. The curable composition according to claim 1, wherein the curable composition is a sealing material, an adhesive, and / or a paint.