JP2004124093A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which has excellent storage stability, sufficient matte effect and stain resistance and improved weather resistance after storage without detriment to properties necessary as a sealing agent, an adhesive, or a coating material. <P>SOLUTION: The curable composition contains (A) a crosslinkable silyl-containing organic polymer, (B) an acrylic polymer, a compound which reacts with water to form an amine compound, and (D) a curing catalyst. It is desirable to use as component (A) a crosslinkable silyl-containing polyoxyalkylene polymer, a crosslinkable silyl-containing acrylic-modified polyoxyalkylene polymer and/or a crosslinkable silyl-containing methacrylic-modified polyoxyalkylene polymer. To further improve weather resistance, it is desirable to use (A1) a crosslinkable silyl-containing acrylic polymer. <P>COPYRIGHT: (C)2004,JPO

Description

(4) The present invention relates to a curable composition, and more particularly, to a curable composition having excellent weather resistance and design.

Room-temperature curable compositions have been used as sealants and adhesives, but excessively glossy conditions are inconvenient because they cause problems in design, such as giving a sense of cheapness. Various matte treatments have been considered.

As a conventional matting treatment, fillers and porous substances having a relatively large particle size have been added.However, the addition of the fillers and the porous substances deteriorates the physical properties as a sealing material, such as a decrease in tensile properties. Sometimes a problem occurred.

As a countermeasure against the above problem, for example, Patent Document 1 discloses a matte sealing material, a polymer of propylene oxide having a crosslinkable hydrolyzable silyl group at a terminal, and a melting point of 10 to 200 ° C. At least one selected from the group consisting of an amine compound, an amide compound having a melting point of 10 to 200 ° C, a fatty acid having a melting point of 10 to 200 ° C, an alcohol having a melting point of 10 to 200 ° C, and a fatty acid ester having a melting point of 10 to 200 ° C. A room temperature curable composition comprising a compound is disclosed. However, the room temperature-curable composition as described above has no problem in matting effect, but it is difficult to sufficiently obtain weather resistance. Further, Patent Document 2 discloses a highly weatherable matte sealing material composition comprising a crosslinkable organic polymer, a photocurable compound, and a compound which reacts with water to produce a primary and / or secondary amine. Although disclosed, the sealing material composition required a photocurable composition, and sufficient weather resistance was not obtained. As a method for improving weather resistance, a method of adding an acrylic polymer is known (for example, see Patent Document 3).
JP-A-9-100408 JP 2001-262125 A JP 2001-207157 A JP-A-52-73998 JP-A-55-9669 JP-A-59-122541 JP-A-60-6747 JP-A-61-233043 JP-A-63-112642 JP-A-3-79627 JP-A-4-283259 JP-A-5-70531 JP-A-5-287186 JP-A-11-80571 JP-A-11-116763 JP-A-11-130931 JP-A-59-78223 JP-A-60-228516 JP-A-59-168014 JP-A-61-34067 JP-A-61-133201 JP-A-6-219922 JP-A-11-80250 JP-A-11-80570 JP-A-11-32312 JP 2000-345136 A JP-A-1-297410 JP-A-7-305018 JP-A-8-127765 JP 2001-40037 A JP 2003-155469 A Japanese Patent Publication No. 45-36319 Japanese Patent Publication No. 46-12154 JP-B-46-30711 Japanese Patent Publication No. 48-36960

The present inventors have conducted various studies in order to obtain a curable composition having a sufficient matting effect and having excellent weather resistance. For example, a method of adding an acrylic polymer to a matte sealing material as disclosed in Patent Document 1 in order to improve weather resistance has been tried. The product has a matting effect, but it has been found that the matting effect is significantly reduced by storing it for a long time, and that it also has an adverse effect on the performance such as antifouling properties, water resistance, and curing properties after storage did.

Usually, a curable composition such as a sealing material is often stored for a long period of time from production to use, and the performance immediately after production is maintained even when a user uses the curable composition. It is particularly problematic that performance such as matting effect and curing characteristics is greatly reduced after storage.

The present invention provides a curable composition having excellent storage stability, sufficient matting effect and antifouling property even after storage, and improved weatherability without impairing the properties as a sealing material, an adhesive and a coating material. The purpose is to provide things.

In order to solve the above-mentioned problems, a first embodiment of the curable composition of the present invention comprises reacting (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, and (C) water. It is characterized by containing a compound that produces an amine compound and (D) a curing catalyst.

The second embodiment of the curable composition of the present invention includes (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, (C1) an amine compound, (C2) a carbonyl compound, and (D) It is characterized by containing a curing catalyst.

In the first and second embodiments of the curable composition of the present invention, as the component (A), a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer, It is preferable to use a methacryl-modified polyoxyalkylene polymer containing a crosslinkable silyl group.

In the first and second aspects of the curable composition of the present invention, by using (A1) a crosslinkable silyl group-containing acrylic polymer as the component (A), weather resistance can be further improved. preferable.

に お い て In the first and second aspects of the curable composition of the present invention, it is preferable to use a (meth) acrylate-fluoroolefin copolymer as the component (B).

A third embodiment of the curable composition of the present invention comprises (A1) a crosslinkable silyl group-containing acrylic polymer, (C) a compound which reacts with water to form an amine compound, and (D) a curing catalyst. It is characterized by doing.

に お い て In the first to third aspects of the curable composition of the present invention, the amine compound is preferably a primary and / or secondary amine. Further, when the amine compound is an aliphatic amine, the matting effect increases before and after storage, which is preferable.

When the compound (E) which reacts with water to form an amine compound having at least one alkoxysilyl group in one molecule is further added to the first to third embodiments of the curable composition, the curing properties after storage This is preferable because it is possible to prevent a decrease in water resistance and to improve the water resistance after storage.

Further, when the (E1) amine compound having at least one alkoxysilyl group in one molecule and the (E2) carbonyl compound are further added to the first to third aspects of the curable composition, the curability after storage can be improved. This is preferable because it is possible to prevent a decrease and to improve the water-resistant adhesion after storage.

Further, it is preferable to further add (F) an epoxy resin to the first to third aspects of the curable composition, since the water resistance can be improved.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability, does not impair the physical properties required as a sealing material such as workability and durability, an adhesive and a coating material, and has a sufficient matting effect and antifouling property even after storage. Thus, a curable composition having improved weather resistance can be provided.

Embodiments of the present invention will be described below, but these embodiments are illustratively shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

A first embodiment of the curable composition of the present invention is a curable composition containing the following components (A), (B), (C) and (D).
(A) a crosslinkable silyl group-containing organic polymer,
(B) an acrylic polymer,
(C) a compound which reacts with water to produce an amine compound, and (D) a curing catalyst

In the present invention, as the crosslinkable silyl group-containing organic polymer used as the component (A), conventionally known crosslinkable organic polymers can be widely used, and a rubber-like cured product which is crosslinked by forming a siloxane bond in the molecule is formed. Is not particularly limited as long as it is an organic polymer containing one or more silyl groups. Examples of such a crosslinkable silyl group-containing organic polymer (A) include those disclosed in Patent Documents 4 to 16. Specific examples of the crosslinkable silyl group-containing organic polymer (A) include a polyoxy group containing one or more crosslinkable silyl groups in the molecule, and a main chain each of which may contain an organosiloxane. Examples thereof include an alkylene polymer, a vinyl-modified polyoxyalkylene polymer, a vinyl polymer, a polyester polymer, an acrylate polymer, a methacrylate polymer, and copolymers and mixtures thereof. It is preferable that 1 to 5 crosslinkable silyl groups be contained in the molecule from the viewpoint of the curability of the sealing material, the physical properties after curing, and the like. Further, the crosslinkable silyl group is preferably a compound represented by the following general formula (1), which is easily crosslinked and easily produced.

(Wherein, R ¹ is 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, and most preferably a methyl group. The reactive group shown is a group selected from a halogen atom, 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, and In the case of X, X may be the same or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, and 1 Is most preferred.)

The main chain of the crosslinkable silyl group-containing organic polymer (A) may be a polyoxyalkylene polymer and / or a polyoxyalkylene polymer, which may contain an organosiloxane, from the viewpoint of physical properties such as tensile adhesion and modulus after curing. Vinyl-modified polyoxyalkylene polymers are preferred. In particular, as the component (A), a polyoxyalkylene-based polymer or an acryl-modified polyoxyalkylene-based polymer containing one or more crosslinkable silyl groups in the molecule and whose main chains may each contain an organosiloxane. A polymer and / or a methacryl-modified polyoxyalkylene polymer and a mixture thereof are preferable, and a polyoxypropylene polymer and an acryl-modified polyoxypropylene polymer whose main chains may each contain an organosiloxane. Those which are coalesced and / or methacryl-modified polyoxypropylene-based polymers are more preferred.

The above-mentioned vinyl-modified polyoxyalkylene-based polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing an organosiloxane contains one or more crosslinkable silyl groups in the molecule. In the presence of a polyoxyalkylene polymer which may contain an organosiloxane, one or more vinyl monomers may be added by a conventional radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation. It can be obtained by polymerizing the product (Patent Documents 17 and 18 and the like are cited as reference, but not limited thereto).

The vinyl monomer is a compound having one or more polymerizable unsaturated bonds in the molecule, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid , Vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate , Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylic acid Amide, n-methylol acrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxy Bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, triacrylate Methylol propantria crele G, ethoxylated isocyanuric acid triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, polyurethane diacrylate Acrylate, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate acrylate, dimer acrylic acid, 2-hydroxy-3-phenoxypropyl acrylate, polyester polyacrylate, 1,6-hexanediol diacrylate, 2- (2- Ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydroph Furyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, zinc diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, pentaacrylate ester, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , Lauryl methacryle G, polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate , Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc dimethacrylate, trimethylolpropane trimethacrylate, and compounds represented by the following chemical formulas (2) to (25) And the like, but are not limited thereto.

The vinyl monomer is used in an amount of 0.1 to 1000 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer which may contain an organosiloxane. Is preferred. The vinyl-modified polyoxyalkylene polymer having one or more crosslinkable silyl groups in the molecule and optionally containing the organosiloxane includes one or more crosslinkable silyl groups in the molecule. A polyoxyalkylene polymer which may contain an organosiloxane and a polymer obtained by polymerizing at least one of the vinyl monomers, and a crosslinkable polymer obtained by introducing a crosslinkable silyl group into the polymer. What blended with the hydrophilic silyl group-containing vinyl polymer can also be used.

候 Also, by using (A1) a crosslinkable silyl group-containing acrylic polymer as the component (A), the weather resistance is improved, which is preferable. (A1) As the crosslinkable silyl group-containing acrylic polymer, conventionally known ones can be widely used and are not particularly limited, and examples thereof include those disclosed in Patent Documents 14 and 19 to 26. . Specifically, the main chain is essentially (meth) acrylic acid, (meth) acrylate, having one or more crosslinkable silyl groups in the molecule, each of which may contain an organosiloxane. Examples of the composition include a compound which is a polymer obtained by (co) polymerizing one or more acrylic monomers such as (meth) acrylonitrile and (meth) acrylamide, and a composition mainly containing a mixture thereof. The acrylic monomer is not particularly limited, but is preferably a (meth) acrylate.

Examples of the acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, -n- (meth) acrylate Hexyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Isodecyl, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and (meth) Alkyl (meth) acrylates such as stearyl acrylate; cycloaliphatic alkyl acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate; phenyl (meth) acrylate , Aromatic acrylates such as toluyl (meth) acrylate and benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) Hydroxyalkyl (meth) acrylate such as ε-caprolactone addition product of hydroxyethyl acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-aminoethyl (meth) acrylate , Dimethyl amide (meth) acrylate Heteroatom-containing acrylates such as noethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. However, it is not limited to these. One or more of these may be used in combination. Among the above (meth) acrylates, butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred because a polymer having a low glass transition temperature can be obtained.

As the component (A1), it is also possible to copolymerize a monomer copolymerizable therewith in addition to the acrylic monomer. Examples of the copolymerizable monomer include, but are not particularly limited to, vinyl monomers such as fluoroolefins, α-olefins, vinyl esters, and vinyl ethers. As the component (A1), the crosslinkable silyl group-containing acrylic polymer and another polymer such as the crosslinkable silyl group-containing polyoxyalkylene polymer and the crosslinkable silyl group-containing vinyl-modified polyoxy as described above. It is also possible to use a mixture with an alkylene polymer or the like, which is included in the present invention. When a mixture of a crosslinkable silyl group-containing acrylic polymer and another polymer is used, the blending ratio of the crosslinkable silyl group-containing acrylic polymer in the mixture is preferably 30% by mass or more.

In the present invention, the crosslinkable silyl group-containing organic polymer (A) having a number average molecular weight of 1,000 or more, particularly 6,000 to 30,000, and having a narrow molecular weight distribution is easy to handle because the viscosity before curing is low, and the strength after curing. Physical properties such as elongation, modulus and the like are suitable. The above component (A) may be used alone or in combination of two or more.

候 In the present invention, by containing the acrylic polymer (B), the weather resistance is improved. The above component (B) can also be used as a plasticizer. As the acrylic polymer used as the component (B), conventionally known polymers can be widely used, and acrylic polymers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide can be used. It is not particularly limited as long as it is an acrylic (co) polymer obtained by polymerizing one or more kinds selected from monomers, and as a preferred example, a (meth) acrylic acid ester monomer as a main component, An acrylate having 1 to 20 carbon atoms in the ester portion is exemplified. Examples include, but are not limited to, the (meth) acrylate monomers described above in component (A1).

The acrylic polymer (B) may not contain a crosslinkable silyl group or may contain a crosslinkable silyl group, and is not particularly limited. On average, the number is preferably 0.05 or more and 2.0 or less, more preferably 0.1 or more and 1.0 or less in the molecule. The acrylic polymer having a crosslinkable silyl group is not particularly limited, and examples thereof include those disclosed in Patent Documents 30 and 31.

In addition, the acrylic polymer (B) may be copolymerized with a monomer copolymerizable therewith, in addition to the acrylic monomer. Examples of the copolymerizable monomer include vinyl monomers such as fluoroolefins, α-olefins, vinyl esters, and vinyl ethers. In particular, a (meth) acrylate-fluoroolefin copolymer containing a (meth) acrylate monomer and a fluoroolefin monomer as main constituent monomers is preferably used. As the (meth) acrylate-fluoroolefin copolymer, conventionally known copolymers can be widely used, and examples thereof include those disclosed in Patent Documents 25 to 29. Examples of the fluoroolefin monomer include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoro (alkyl vinyl ether). Among these, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and trifluoroethylene are preferred from the viewpoint of polymerizability, and more preferred are tetrafluoroethylene, chlorotrifluoroethylene and trifluoroethylene.

The acrylic polymer (B) can be produced by a usual method such as suspension polymerization or emulsion polymerization in an aqueous medium, solution polymerization in an organic solvent, or bulk polymerization. As the organic solvent, commonly used organic solvents can be used, for example, cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone And ketones such as cyclohexanone; alcohols such as methanol, ethanol and isopropanol; and one or more of these can be used.

Examples of the radical-generating polymerization initiator used in the polymerization include peroxides such as diisopropyl peroxydicarbonate, tertiary butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide, and ditertiary butyl peroxide, or azobisisopropane. Azo compounds such as butyronitrile and azobisisovaleronitrile, and inorganic peroxides such as ammonium persulfate and potassium persulfate can be used. It is preferable not to use a chain transfer agent because it leads to a decrease in weather resistance.

The above polymerization is carried out at a polymerization temperature of 20 ° C. to 350 ° C., preferably 150 ° C. to 350 ° C., at a pressure of normal pressure to 10 MPa, and in the case of pressurization, using a pressure resistant autoclave for a reaction time of 5 minutes to 20 hours. be able to. The polymerization method may be batch polymerization, semi-batch polymerization, or continuous polymerization.

ガ ラ ス The glass transition temperature of the acrylic polymer (B) is preferably 10 ° C or lower, more preferably 0 ° C or lower, and even more preferably -10 ° C or lower. Further, the weight average molecular weight is preferably 500 or more and 20,000 or less, more preferably 700 or more and 10,000 or less. When the glass transition temperature is higher than 10 ° C., workability at a low temperature deteriorates. On the other hand, if the weight average molecular weight exceeds 20,000, sufficient plasticity will not be exhibited, resulting in poor workability. On the other hand, if the weight average molecular weight is less than 500, low molecular polymers will bleed, resulting in reduced contamination.

The blending ratio of the component (B) is not particularly limited, but the component (B) is preferably used in an amount of 1 to 400 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the component (A). Is more preferable. The acrylic polymers may be used alone or in combination of two or more.

As the compound which reacts with water to generate an amine compound used as the component (C), specifically, the amine compound is preferably selected from the viewpoints of easy availability of raw materials, storage stability, and reactivity with water. Suitable examples include ketimine compounds, enamine compounds, and / or aldimine compounds.

The above ketimine compound, enamine compound and aldimine compound can each be obtained by the dehydration reaction of (C1) amine compound and (C2) carbonyl compound. The method for producing the component (C) is not particularly limited, and a known method can be used.

ア ミ ン The component (C1) amine compound is not particularly limited, and examples thereof include primary and / or secondary amines. In particular, when the component (C1) amine compound is an aliphatic amine, the matting effect is increased before and after storage, which is preferable.

The primary and / or secondary amine is not particularly limited. Examples of the primary amine include butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, and 3-methoxy as monoamines. Propylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, trimethylcyclohexylamine, benzylamine, aniline and the like can be mentioned. As the diamine, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino Ndecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18- Diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,21-diaminohenticosan, 1,22-diaminodocosan, 1,23-diaminotricosan, 1,24-diaminotetra Kosan, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, Diaminodiethylphenylmethane, polyoxy Ethylenediamine, polyoxypropylene diamine can be cited, as a polyamine, such as hexane tri (methylamino) can be exemplified. Examples of the secondary amine include monoamines such as dilaurylamine, distearylamine and methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-distearylbutylamine and N-butyl-N'-. Examples thereof include diamines such as laurylethylamine, N-butyl-N'-laurylpropylamine, and N-lauryl-N'-stearylbutylamine. Examples of the primary and secondary mixed amines include N-lauryl propylene diamine and N-stearyl propylene diamine. Examples of the primary and secondary mixed polyamines include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. In particular, aliphatic amines such as stearylamine, hexamethylenediamine, and N-stearylpropylenediamine have more matting effects and are preferred.

The component (C1) amine compound has a melting point of 35 ° C. or more or one or more nitrogen atoms and two or more nitrogen atoms in the molecule in order to significantly reduce the gloss and gloss of the cured surface of the sealing material. Those containing atom-bonding active hydrogen are suitable because they have a large matting effect and are excellent in design. Those having a melting point of less than 35 ° C. tend to soften at heat resistance, especially at high temperatures in the summer, and those having a melting point of more than 100 ° C. tend to have a hard and brittle sealing material surface and easily impair the elasticity which is a basic property of the sealing material. Therefore, the component (C1) amine compound preferably has a melting point of 35 ° C. or more, particularly preferably 40 to 100 ° C.

The component (C2) carbonyl compound includes known compounds such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-amylaldehyde, isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, and phenylacetaldehyde. Aldehydes; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, and trimethylcyclohexanone; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl-tert-butyl ketone, and diethyl ketone , Dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, etc. Ketones; aromatic ketones such as acetophenone, benzophenone and propiophenone; and the following general formula (26) such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methylethyl malonate, and dibenzoylmethane. )), But are not limited thereto. Among them, methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde, and a β-dicarbonyl compound having an active methylene group [compound represented by the following general formula (26)] are more preferable.

[Wherein, R ² and R ³ are the same or different and each have an alkyl group having 1 to 16 carbon atoms (eg, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl, hexadecyl, etc.) ), An aryl group having 6 to 12 carbon atoms (eg, phenyl, tolyl, hexyl, naphthyl, etc.) or an alkoxyl group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, prooxy, butoxy, etc.). ]

The compounding ratio of the component (C) is such that the amine compound formed by reacting with water is 0.05 to 50 parts by weight, particularly 0.1 to 50 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer (A). It is preferable to mix so as to be 20 parts by weight. The above compounds which react with water to form an amine compound may be used alone or in combination of two or more.

The curing catalyst used as the component (D) is not particularly limited as long as it exhibits a function of the curing catalyst with respect to the component (A). Examples thereof include organometallic compounds and amines. It is preferable to use a condensation catalyst. Examples of the silanol condensation catalyst include, for example, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate Organic tin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; reactants of dibutyltin oxide with phthalic acid esters; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum Organic aluminum compounds such as trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Co tetra acetylacetonate, chelate compounds such as titanium tetraacetyl acetonate; lead octylate; silanol condensation catalyst as known other acidic catalysts and basic catalysts, and the like. Of these, dibutyltin diacetylacetonate is particularly preferred because it is a liquid having a high crosslinking rate, toxicity and relatively low spontaneity.

The mixing ratio of the component (D) is from 0.1 to 30 parts by weight, especially from 0.1 to 30 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer (A) from the viewpoint of the crosslinking rate, the physical properties of the cured product, and the like. It is preferable to use 5 to 20 parts by weight. These curing catalysts may be used alone or in combination of two or more.

The curable composition of the present invention further comprises (E) reacting with water and reacting with water to prevent at least one of the curability of the composition from deteriorating after storage and to improve the water resistance after storage. It is preferable to add a compound that produces an amine compound having an alkoxysilyl group. In the present invention, the deterioration of the curing characteristics such as the curing speed after storage and the hardness and thickness of the cured product is referred to as the deterioration of the curing characteristics. Specific examples of the compound (E) which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule include the availability of raw materials, storage stability, and reactivity with water. From these viewpoints, preferred examples include ketimine compounds, enamine compounds, and / or aldimine compounds, which are amine compounds having at least one alkoxysilyl group in one molecule.

The ketimine compound, enamine compound and aldimine compound can be obtained by the dehydration reaction between (E1) an amine compound having at least one alkoxysilyl group in one molecule and (E2) a carbonyl compound. The method for producing the component (E) is not particularly limited, and a known method can be used.

脱水 The dehydration reaction product of the amine compound having at least one alkoxysilyl group in one molecule of the component (E1) and the carbonyl compound of the component (E2) will be described as follows. The amine compound having an alkoxysilyl group as the component (E1) is not particularly limited, and examples thereof include compounds represented by the following general formula (27).

[In the formula (27), n = 0, 1, 2, R ⁴ and R ⁵ are the same or different and each is a hydrocarbon group having 1 to 4 carbon atoms, and R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms. The group, Z, represents a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms. ]

Here, examples of R ⁴ and R ⁵ include an alkyl group such as methyl, ethyl, propyl and butyl, and an alkenyl group such as vinyl, allyl, propenyl and butenyl, and an alkyl group is particularly preferable. Examples of R ⁶ include an alkylene group such as methylene, ethylene, propylene, and butylene, an arylene group such as phenylene, and an alkylene arylene group. An alkylene group is particularly preferable. n is preferably 0 or 1.

Specific examples include compounds represented by the following formulas (28) to (35), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl Examples thereof include aminosilanes represented by methyldimethoxysilane and the like. Among them, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and the like are preferable.

The component (E2) carbonyl compound is not particularly limited, and a carbonyl compound exemplified in the description of the component (C2) is used.

The method for producing the compound (E) used in the present invention, which produces an amine compound having at least one alkoxysilyl group in one molecule by reacting with water, may be any method, but has a monomer purity of 50 to 95%. The following method is desirable for producing a product having an amino group blocking ratio of 90% or more. In the reaction between the amine compound having an alkoxysilyl group and the carbonyl compound, an amine compound having an alkoxysilyl group is introduced into the carbonyl compound under heating, and water generated during the introduction is azeotropically distilled off together with the carbonyl compound. In this case, it is preferable to react an excess amount of the carbonyl compound with the amine compound having an alkoxysilyl group.

Further, the introduction temperature (reaction temperature) of the amine compound having an alkoxysilyl group is preferably from about the azeotropic temperature of the carbonyl compound to water to about the reflux temperature of the carbonyl compound. It is preferable to introduce in this temperature range. For example, when the carbonyl compound is methyl isobutyl ketone and this is reacted with an amine compound having an alkoxysilyl group, the azeotropic temperature of methyl isobutyl ketone and water becomes about 80 ° C., and the reflux temperature of this methyl isobutyl ketone becomes Since the temperature is 130 ° C., the introduction temperature of the amine compound having an alkoxysilyl group may be set to 80 to 130 ° C. The method of introducing the amine compound having an alkoxysilyl group for this reaction is optional, but it is preferable to introduce it into the liquid in order to react it with the carbonyl compound quickly. Although the introduction time is optional, it is preferably about 30 minutes to 20 hours. In addition, this reaction is preferably performed under an inert gas such as nitrogen or argon since the reaction product is hydrolyzed in the presence of moisture, and the water content in the carbonyl compound should be as small as possible. preferable.

(E) The production of a compound which produces an amine compound having at least one alkoxysilyl group in one molecule by reacting with water can be carried out, as described above, by adding an amine compound having an alkoxysilyl group to a carbonyl compound under heating as described above. The reaction is carried out, and water generated during the introduction is azeotropically distilled off together with the carbonyl compound.However, even after the completion of the introduction of the amine compound having an alkoxysilyl group, water in the system is removed due to distillation. Is preferably azeotropically distilled with a carbonyl compound.

The distillation temperature is raised to the reflux temperature of the carbonyl compound, and the distillation is continued for about 30 minutes to 2 hours after the reflux temperature is reached, or the system is concentrated by vacuum concentration immediately after the completion of the introduction of the amine compound having an alkoxysilyl group. Preferably, unreacted carbonyl compounds are distilled off. In addition, if the distillation is continued for about 30 minutes to 2 hours after the reflux temperature is reached, water is not left in the system, and this is stable and progress of hydrolysis condensation does not easily occur. It is preferable to distill it out of the system. The compound obtained by such a method, which reacts with water of interest to form an amine compound having at least one alkoxysilyl group in one molecule, is combined with an alkoxysilane oligomer formed by hydrolytic condensation of an alkoxy group. Although it is obtained as a mixture, the amount of oligomer is smaller than that of a conventional production method, and the amount of residual amino groups is also smaller. In order to obtain this compound with high purity, a compound which reacts with water to form an amine compound having at least one alkoxysilyl group in one molecule can be isolated by distillation. These are not desirable for use in the curable compositions of the present invention because of their high cost and poor adhesion.

In the present invention, as the compound (E) which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule, the monomer purity obtained by the above method or the like is 50 to 95%, It is preferably 70-95%, more preferably 80-95%, and the amino group blocking ratio is 90% or more, preferably 95% or more. When the monomer purity is lower than 50%, the storage stability of the composition is poor. When the monomer purity is higher than 95%, the adhesion of the composition is poor. When the amino group blocking ratio is lower than 90%, the storage stability of the composition is low. Is not preferred because it becomes worse.

The mixing ratio of the component (E) is not particularly limited, but is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the component (A). preferable. These compounds which react with water to form an amine compound having at least one alkoxysilyl group in one molecule may be used alone or in combination of two or more.

The curable composition of the present invention contains (E1) an amine having at least one alkoxysilyl group in one molecule, in order to prevent a decrease in curing properties after storage and to improve water resistance after storage. It is preferable to further add the compound and the (E2) carbonyl compound. As the component (E1) and the component (E2), the amine compound and the carbonyl compound each having at least one alkoxysilyl group in one molecule described in the description of the component (E) can be similarly used. The components (E1) and (E2) cause a dehydration reaction in the blend. The dehydration reaction may be subjected to a reaction treatment such as a heat treatment, if necessary, but can be allowed to proceed over time without performing a special step.

The mixing ratio of the above components (E1) and (E2) is not particularly limited, but the components (E1) and (E2) are each 0.05 to 50 parts by weight, especially 0 to 100 parts by weight of the component (A). It is preferable to mix them in an amount of 0.1 to 20 parts by weight. Further, [molar amount of component (E1)] / [molar amount of component (E2)] is preferably in the range of 0.1 to 5.0, and more preferably in the range of 0.5 to 2.0. More preferred. The amine compound and the carbonyl compound may be used alone or in combination of two or more.

硬化 It is preferable to further add (F) an epoxy resin to the curable composition of the present invention in order to improve water resistance. As the epoxy resin (F), conventionally known epoxy resins can be widely used and are not particularly limited. However, it is preferable to use a bisphenol type epoxy resin or an epoxy resin having a polyoxyalkylene skeleton. The epoxy resin having a polyoxyalkylene skeleton is not particularly limited as long as it has a polyalkylene oxide.Bisphenol A, bisphenol F, bisphenol AD, and an epoxy resin having a polyoxyalkylene unit including novolak and the like are more preferable. A preferred example is given.

The epoxy resin (F) is preferably used in an amount of 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, per 100 parts by weight of the component (A). The epoxy resins may be used alone or in combination of two or more.

(4) When the component (F) epoxy resin is added, ketimines and the like may be added as a curing agent (epoxy resin curing agent) for the epoxy resin. The above curing agents may be used alone or in combination of two or more. Of course, it is of course possible to use a curing catalyst which acts as a curing agent for the epoxy resin and has a curing catalytic action on the component (A) as the curing catalyst (D) and the curing agent.

The curable composition of the present invention may further comprise, in addition to the components described above, an adhesion promoter, a physical property modifier, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), Substances such as imparting agents, anti-sagging agents, ultraviolet absorbers, antioxidants, flame retardants, coloring agents, radical polymerization initiators and various solvents such as toluene and alcohol may be blended, and other compatible heavy metals Coalescing may be blended.

各種 As the other compatible polymer, various polyethers are particularly preferable, and in particular, polyethers having a silicon functional group proposed in Patent Document 4 and 32-35 are exemplified.

Examples of the adhesion-imparting agent include various silane coupling agents, for example, aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Epoxy silanes such as methoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane, etc. Can be The above-mentioned adhesion imparting agents may be used alone or in combination of two or more.

The above physical property modifier is added for the purpose of improving tensile properties. Examples of the physical property modifier include a silicon compound having one silanol group in one molecule. Examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, and diphenylalkylsilanol. Various silane coupling agents such as a silicon compound which decomposes to form a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, and diphenylalkylmethoxy Examples include silane, triphenylethoxysilane, and trialkylethoxysilane. The physical property modifiers may be used alone or in combination of two or more.

The above filler is added for the purpose of reinforcing the cured product. As the filler, for example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, silicic anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, zeolite And the like. Of these, calcium carbonate is preferred, and fatty acid-treated calcium carbonate is more preferred. Further, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, Saran balloons, acrylic balloons, and the like can also be used. Among them, an acrylic balloon is more preferable in that the decrease in elongation after curing of the composition is small. The above fillers may be used alone or in combination of two or more.

The above plasticizer is added for the purpose of enhancing elongation properties after curing and enabling reduction in modulus. In the present invention, the above component (B) can be used as a plasticizer, but other plasticizers may be added as necessary. Other plasticizers include, for example, phosphoric esters such as tributyl phosphate and tricresyl phosphate; phthalic esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate; fatty acids such as glycerin monooleate; Monobasic acid esters; fatty acid dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycol esters such as polypropylene glycol; aliphatic esters; epoxy plasticizers; polyester plasticizers; And the like. The plasticizers may be used alone or in combination of two or more.

Examples of the thixotropic agent include colloidal silica, inorganic thixotropic agents such as asbestos powder, organic bentonite, modified polyester polyols, organic thixotropic agents such as fatty acid amides, hydrogenated castor oil derivatives, fatty acid amide wax, aluminum stearylate And barium stearylate. The thixotropic agents may be used alone or in combination of two or more.

The above dehydrating agent is added for the purpose of removing water during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.

The antioxidant is used for preventing the cured sealing material from oxidizing and improving weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine antioxidant include N, N ', N ", N" "-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine.N, N'-bis- (2,2,6 Polycondensate of 2,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (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- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decandioate- 1 (octyloxy) -4-piperidyl) ester, reaction product of octane with 1,1-dimethylethyl hydroperoxide (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenolic antioxidants include pentane Eristol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-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-hydroxyphenylpropioamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester of benzenepropanoic acid, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium M-diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzeneamine Reaction product of 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 with 2,4,4-trimethylpentene Triazin-2-ylamino) phenol and the like, but not limited thereto. The above antioxidants may be used alone or in combination of two or more.

The above-mentioned ultraviolet absorber is used for preventing the photo-deterioration of the cured sealing material and improving the weather resistance. For example, a benzotriazole-based, triazine-based, benzophenone-based, benzoate-based ultraviolet absorber, etc. And the like. Examples of the UV absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and branched dodecyl) -4 Benzotriazole-based ultraviolet absorbers such as -methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(f Triazine-based ultraviolet absorbers such as (sil) oxy] -phenol, benzophenone-based ultraviolet absorbers such as octabenzone, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Examples include, but are not limited to, benzoate UV absorbers. The ultraviolet absorbers may be used alone or in combination of two or more.

The second embodiment of the curable composition of the present invention includes (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, (C1) an amine compound, (C2) a carbonyl compound, and (D) It is characterized by containing a curing catalyst.

The components (A), (B) and (D) are as described above in the first embodiment of the curable composition of the present invention. The mixing ratio of the components (B) and (D) may be the same as in the above-described first embodiment of the curable composition of the present invention. As the component (C1) and the component (C2), the amine compound and the carbonyl compound described in the component (C) of the first embodiment of the curable composition of the present invention can be used in the same manner. A second embodiment of the curable composition of the present invention is one in which components (C1) and (C2) are subjected to a dehydration reaction in a formulation. The dehydration reaction may be subjected to a reaction treatment such as a heat treatment, if necessary, but can be allowed to proceed over time without performing a special step. The mixing ratio of the components (C1) and (C2) is not particularly limited, but the components (C1) and (C2) are each 0.05 to 50 parts by weight, particularly 0.1 to 100 parts by weight, based on 100 parts by weight of the component (A). It is preferable to mix them in an amount of 1 to 20 parts by weight. Further, [molar amount of component (C1)] / [molar amount of component (C2)] is preferably in the range of 0.1 to 5.0, and more preferably in the range of 0.5 to 2.0. More preferred. The amine compound and the carbonyl compound may be used alone or in combination of two or more. If necessary, the above-described plasticizer may be added. The composition other than the above components is the same as in the first embodiment.

The third embodiment of the curable composition of the present invention comprises a component (A1) a crosslinkable silyl group-containing acrylic polymer, a component (C) a compound which reacts with water to form an amine compound, and a component (D) cured. It is characterized by containing a catalyst. The components (A1), (C) and (D) are as described above in the first embodiment of the curable composition of the present invention. The mixing ratio of each component may be the same as in the above-described first embodiment of the curable composition of the present invention. If necessary, the above-described plasticizer may be added. The same applies to compounds other than the above components.

A fourth embodiment of the curable composition of the present invention comprises a component (A1) a crosslinkable silyl group-containing acrylic polymer, a component (C1) an amine compound, a component (C2) a carbonyl compound, and a component (D) a curing catalyst. It is characterized by containing. The components (A1) and (D) are as described above in the first embodiment of the curable composition of the present invention, and the blending ratio of the component (D) is the same as that of the first curable composition of the present invention. This may be performed in the same manner as described above. The components (C1) and (C2) are as described above in the second embodiment of the curable composition of the present invention, and the blending ratio of the components (C1) and (C2) is also the above-described curable composition of the present invention. What is necessary is just to carry out similarly to the 2nd aspect of a thing. If necessary, the above-described plasticizer may be added. The same applies to compounds other than the above components.

硬化 The curable composition of the present invention can be of a one-pack type or a two-pack type as required, but it can be suitably used particularly as a one-pack type. The curable composition of the present invention is suitably used as a sealing material, an adhesive, a coating material, and the like. The curable composition of the present invention has excellent weather resistance and design properties without impairing the basic performance, and is particularly preferably used for sealing outer wall materials. It can be used for applications, civil engineering, electric / electronic fields, etc.

す る Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the Examples are illustrative and should not be construed as limiting.

(Synthesis Examples 1 and 2)
Synthesis was performed using the compounding substances and compounding amounts (g) shown in Table 1. After the heated and dissolved primary amine was placed in a heating device and a stirring vessel equipped with an ester tube, the carbonyl compound was added with stirring. Toluene was further added thereto, followed by heating and stirring at 110 to 150 ° C. for 3 hours, and water was dehydrated by an ester tube. Then, the pressure was reduced to remove the excess carbonyl compound and toluene to obtain a ketimine compound.

The amount of each compounded substance in Table 1 is indicated by (g), and * 1 to * 3 are as follows.
* 1: Stearylamine (manufactured by Kao Corporation, Farmin 80, amine value 207)
* 2: Hexamethylene diamine (molecular weight: 116)
* 3: Methyl isobutyl ketone (4-methyl-2-pentanone, molecular weight: 100.2)

(Synthesis example 3)
As a crosslinkable silyl group-containing acrylic polymer (A1), a crosslinkable silyl group-containing acrylate-fluoroolefin copolymer was synthesized based on the following method. In a 2-liter autoclave equipped with a stirrer, 135 g of butyl acetate and 75 g of ethanol as organic solvents, 6.9 g of butyl acrylate, 7.0 g of 2-methoxyethyl acrylate and vinyl trimethoxysilane as monomers. Then, 0 g and 4.0 g of ethoxyethyl peroxydicarbonate as a radical polymerization initiator were charged, and degassing and nitrogen replacement were repeated three times, followed by degassing under reduced pressure, and 510 g of chlorotrifluoroethylene. The temperature was raised to 50 ° C. to start the polymerization, and after 1 hour, a mixed solution of 62.4 g of butyl acrylate, 63.0 g of 2-methoxyethyl acrylate, and 9.0 g of vinyltrimethoxysilane was added for 7 hours. And fed into the autoclave using a pump at a constant speed. After a lapse of 8 hours from the start of the polymerization, the temperature was raised to 60 ° C., the polymerization was performed for a total of 10 hours, and then the system was cooled. After completion of the reaction, unreacted chlorotrifluoroethylene was purged, and the autoclave was opened to obtain a copolymer solution. The resulting solution was filtered to remove sodium borate, dried under reduced pressure, poured into methanol, washed and dried to obtain 245 g of a copolymer.

(Synthesis example 4)
A 2-L pressure autoclave equipped with a stirrer was charged with 200 parts by mass of 2-propanol. Next, degassing and nitrogen replacement were repeated three times, followed by degassing under reduced pressure and heating to 260 ° C. At the time when the temperature rise was completed, 750 parts by mass of butyl acrylate and 130 parts by mass of ethyl acrylate were used as the acrylate monomer, 120 parts by mass of γ-methacryloxypropyltrimethoxysilane, 200 parts by mass of 2-propanol, A mixed solution containing 10 parts by mass of shary butyl peroxide was supplied into the autoclave at a constant rate to start the reaction. Addition and reaction were carried out over 2 hours, and 10 minutes after completion of the addition, the mixture was cooled to 30 ° C., and a crosslinkable silyl group-containing acrylic polymer having an average of 0.72 crosslinkable silyl groups in one molecule (B ) Got. The weight average molecular weight of the obtained polymer was 3,500.

(Example 1)
As shown in Table 2, as the component (A) a crosslinkable silyl group-containing organic polymer, a crosslinkable silyl group-containing polyoxypropylene polymer, as the component (B) an acrylic polymer, a hydroxyl group-free acrylic polymer, and aging Preventive agents, calcium carbonate, and vinyltrimethoxysilane were charged in predetermined amounts, respectively, and mixed under heating and reduced pressure at 110 ° C. for 2 hours to dehydrate the compounded substances. Further, the ketimine compound obtained in Synthesis Example 1 above as a component (C) which reacts with water to produce an amine compound, and dibutyltin diacetylacetonate as a curing catalyst for component (D) and an aminosilane compound are added in predetermined amounts. The mixture was stirred and blended to prepare a curable composition.

The amount of each compounded substance in Table 2 is indicated by (g), * 1 and * 3 are the same as in Table 1, and * 4 to * 17 are as follows.
* 4: Crosslinkable silyl group-containing polyoxypropylene polymer (manufactured by Kanegafuchi Chemical Industry Co., Ltd., trade name: MS Polymer S303)
* 5: Crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer (manufactured by Kaneka Chemical Co., Ltd., trade name: MS Polymer S903)
* 6: Crosslinkable silyl group-containing acrylic polymer obtained in Synthesis Example 3 * 7: Hydroxy group-free acrylic polymer (Toagosei Co., Ltd., trade name: UP-1110)
* 8: Hydroxyl-containing acrylic polymer (Toagosei Co., Ltd., trade name: UH-2000)
* 9: Acrylate-fluoroolefin copolymer (trade name: XCS-3500, manufactured by Toagosei Co., Ltd.)
* 10: Crosslinkable silyl group-containing acrylic polymer obtained in Synthesis Example 4 * 11: Ketimine compound obtained in Synthesis Example 1 * 12: Ketimine compound obtained in Synthesis Example 2 * 13: Dibutyltin diacetylacetonate * 14 : Ketimine structure-containing aminosilane (trade name: X12-817, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 15: γ-aminopropyltrimethoxysilane * 16: Antiaging agent manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin B75
* 17: Calcium carbonate treated with fatty acid (Maruo Calcium Co., Ltd., trade name: Calfine 200M)

(Examples 2 to 4)
As shown in Table 2, a hydroxyl group-containing acrylic polymer (Example 2), an acrylate-fluoroolefin copolymer (Example 3), or a synthetic resin obtained in Synthesis Example 4 was used instead of the hydroxyl group-free acrylic polymer. A curable composition was prepared in the same manner as in Example 1 except that the crosslinkable silyl group-containing acrylic polymer (Example 4) was blended.

(Example 5)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the ketimine compound obtained in Synthesis Example 2 was blended instead of the ketimine compound obtained in Synthesis Example 1.

(Example 6)
As shown in Table 2, except that (A1) a crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer was blended in place of the crosslinkable silyl group-containing polyoxypropylene polymer, a method similar to that of Example 1 was used. A curable composition was prepared.

(Examples 7 and 8)
As shown in Table 2, in place of the aminosilane compound, a ketimine structure-containing aminosilane was compounded as a compound that generates an amine compound having at least one alkoxysilyl group in one molecule by reacting with component (E) water instead of the aminosilane compound. Prepared a curable composition in the same manner as in Example 1 or 6.

(Example 9)
As shown in Table 2, the same as Example 6 except that (A1) the crosslinkable silyl group-containing acrylic polymer obtained in Synthesis Example 3 was blended instead of the crosslinkable silyl group-containing polyoxypropylene polymer. A curable composition was prepared by the method described above.

(Example 10)
As shown in Table 2, as the component (A1) crosslinkable silyl group-containing acrylic polymer, the copolymer obtained in Synthesis Example 3 above, an antioxidant, calcium carbonate, vinyl trimethoxysilane, and dioctyl phthalate were respectively used. A fixed amount was charged, and the mixture was heated and mixed under reduced pressure at 110 ° C. for 2 hours to dehydrate the compounded substance. Further, the ketimine compound obtained in the above Synthesis Example 1 was added as the component (C), and dibutyltin diacetylacetonate and an aminosilane compound were added as the component (D), followed by stirring and mixing to prepare a curable composition.

(Example 11)
As shown in Table 2, as the component (A1), 70 parts by weight of the copolymer obtained in Synthesis Example 3 and polyoxysiloxane containing a crosslinkable silyl group were used instead of 100 parts by weight of the copolymer obtained in Synthesis Example 3. A curable composition was prepared in the same manner as in Example 10, except that 30 parts by weight of the propylene polymer was blended.

(Example 12)
As shown in Table 2, a primary amine, a carbonyl compound, and an aminosilane compound were used instead of the ketimine compound and the ketimine structure-containing aminosilane obtained in Synthesis Example 1 by the same method as in Example 8. A curable composition was prepared.

(Example 13)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 10, except that a primary amine and a carbonyl compound were added instead of the ketimine compound obtained in Synthesis Example 1.

(Comparative Example 1)
As shown in Table 2, the same as Example 1 except that the hydroxyl group-free acrylic polymer and the ketimine compound obtained from Synthesis Example 1 were not blended, and dioctyl phthalate and a primary amine were blended instead. A curable composition was prepared by the method.

(Comparative Example 2)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that a primary amine was used instead of the ketimine compound obtained in Synthesis Example 1.

[performance test]
The following performance tests were conducted on the curable compositions obtained in Examples 1 to 13 and Comparative Examples 1 and 2. Note that 28 days and 56 days at 50 ° C. correspond to 6 to 8 months and 12 to 16 months at normal temperature (20 ° C.). Table 3 shows the measurement results of each performance.

1) Surface Properties The curable composition obtained above (immediately after production and after storage at 50 ° C. for 28 days and 56 days) was cured into a sheet, cured at 23 ° C. and 50% relative humidity for 7 days, and cured. A 5 mm sheet was produced. The gloss of the surface of this sheet was visually determined, and the surface gloss was measured using a 60-degree specular gloss meter. Table 3 shows the results. The smaller the value of the surface gloss, the lower the light reflectance, indicating that the surface gloss is reduced.

(4) The curability composition obtained above (immediately after production and after storage at 50 ° C. for 28 days and 56 days) was examined for contamination by the following method. Using a slate plate with a thickness of 5 mm, a joint having a depth of 5 mm, a width of 25 mm, and a length of 150 mm is prepared, a curable composition is poured into the joint, and an excess curable composition is scraped off with a spatula. Was flattened at 23 ° C. and 50% relative humidity for 7 days to prepare a test body. Black silica sand (particle size: 70 to 110 μm) was sprinkled on the surface of the cured test specimen, the test specimen was immediately turned over, and the bottom was patted lightly with a hand to drop excess black silica sand. The state of the black silica sand (dirt) remaining on the surface was visually observed to determine the contamination after curing. Table 3 shows the results.

2) Tensile adhesiveness A test was conducted in accordance with JIS A1439: 1997 "4.21 Tensile adhesiveness test" of "Testing method for building sealing materials" (test temperature 23 ° C). The test piece was prepared by placing the curable composition obtained as described above (immediately after production and after storage at 50 ° C. for 28 days and 56 days) on anodized aluminum at 23 ° C. and 50% relative. Cured for 14 days at humidity and 14 days at 30 ° C. As for the water-resistant adhesiveness, the test piece prepared under the above conditions was immersed in water at 23 ° C. for 7 days, and the state of destruction was evaluated. Table 3 shows the results.
Adhesion evaluation criteria: ；: cohesive failure, 、: when thin layer cohesive failure is confirmed, Δ: when interfacial fracture is confirmed.

3) Retention rate of touch dry time The touch dry time was measured according to JIS A 1439 4.19. The determination method was as follows: after storage at 50 ° C. for 28 or 56 days / immediately after production: less than 1.3 ◎: 1.3 to less than 1.6 ○: 1.6 to less than 1.9: 1.9 or more was evaluated as x. Table 3 shows the results.

4) Rubber Hardness Retention Rate After 24 hours in an atmosphere of 23 ° C. and 50% relative humidity, test specimens were stacked so that the thickness became 5 mm or more, and JIS K 6301 5.2 Spring type hardness tester A type was used. It measured using. Judgment method was as follows: less than 0.5 after storage / immediately after production / immediately after production for 28 or 56 days, Δ: 0.5 to less than 0.7, O: 0.7 to less than 0.9, 0.9 Not less than 1.0 and not more than ◎. Table 3 shows the results.

5) Weather Resistance The state of the surface of the sealing material after 1000 hours, 2000 hours, 3000 hours, 5000 hours, and 7000 hours was visually determined using a sunshine weatherometer according to JIS K6266: 1996. Table 4 shows the results.
Judgment criteria: ；: no hair crack on sealing material surface, Δ: slight hair crack on sealing material surface, x: many hair cracks on sealing material surface.

A: Immediately after production, b: After storage at 50 ° C. for 28 days, c: After storage at 50 ° C. for 56 days

As shown in Table 3, the surface properties of Examples 1 to 13 were good with respect to gloss, gloss, stainability and adhesion of the surface, both immediately after production and after storage at 50 ° C. for 28 days and 56 days. Was done. In Examples 7 to 9 in which the component (E) was blended and Examples 12 and 13 in which the components (E1) and (E2) were blended, the adhesiveness after storage at 50 ° C. for 28 days and 56 days, particularly The adhesiveness after the water resistance test was improved, and the touch dry time and rubber hardness immediately after production were maintained after storage at 50 ° C. for 28 days and 56 days. On the other hand, in Comparative Example 2 in which the component (C) was not blended, there was no problem in the surface properties immediately after production, but after storage at 50 ° C. for 28 days and 56 days, the surface became glossy and stained, and the glossiness was low. Was also increasing. As shown in Table 4, Examples 1 to 13 had improved weather resistance as compared with Comparative Example 1. In Example 6 and Examples 8 to 13, the weather resistance was particularly improved.

Claims (12)

(A) a crosslinkable silyl group-containing organic polymer,
(B) an acrylic polymer,
A curable composition comprising (C) a compound which reacts with water to produce an amine compound, and (D) a curing catalyst. (A) a crosslinkable silyl group-containing organic polymer,
(B) an acrylic polymer,
(C1) an amine compound,
A curable composition comprising (C2) a carbonyl compound and (D) a curing catalyst. The component (A) is a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing acryl-modified polyoxyalkylene polymer, and / or a crosslinkable silyl group-containing methacryl-modified polyoxyalkylene polymer. The curable composition according to claim 1, wherein the curable composition is provided. The curable composition according to claim 1, wherein the component (A) is (A1) a crosslinkable silyl group-containing acrylic polymer. The curable composition according to any one of claims 1 to 4, wherein the component (B) is a (meth) acrylate-fluoroolefin copolymer. (A1) a crosslinkable silyl group-containing acrylic polymer,
A curable composition comprising (C) a compound which reacts with water to produce an amine compound, and (D) a curing catalyst. (A1) a crosslinkable silyl group-containing acrylic polymer,
(C1) an amine compound,
A curable composition comprising (C2) a carbonyl compound and (D) a curing catalyst. The curable composition according to any one of claims 1 to 7, wherein the amine compound is a primary and / or secondary amine. The curable composition according to any one of claims 1 to 8, wherein the amine compound is an aliphatic amine. The curable composition according to any one of claims 1 to 9, further comprising (E) a compound which reacts with water to form an amine compound having at least one alkoxysilyl group in one molecule. object. The curable composition according to any one of claims 1 to 10, further comprising (E1) an amine compound having at least one alkoxysilyl group in one molecule and (E2) a carbonyl compound. The curable composition according to any one of claims 1 to 11, further comprising (F) an epoxy resin.