JP3499223B2 - Method for producing curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a curable composition having strong thixotropy, which is cured by moisture in the air to form a rubber-like elastic body having good adhesiveness and physical properties. <br /> 2. /> Concerned.

[0002]

2. Description of the Related Art Conventionally, as a moisture-curing resin component used for waterproof sealing materials for buildings, civil engineering, automobiles, adhesives, paints, etc. A resin having a crosslinkable silyl group in the molecule of a chain polyether is widely used because of its excellent workability and adhesiveness.

[0003]

However, elastic adhesives containing modified silicone resin, elastic coatings such as waterproof coatings and floor coatings, putty materials, and sealing materials have relatively low viscosity and are easy to work with. Although it has the advantage that it is easy, the cured product has the disadvantages of lower elongation and brittleness than polyurethane resin, and poor rubber elasticity, and has a large elongation and excellent displacement followability in applications such as buildings, civil engineering, and automobiles. In addition, there is a problem that it is not easily used in places where high rubber elasticity is required, that is, high tensile adhesive strength. In addition, for adhesives, do not slip off when adhering heavy tiles etc. to the wall surface, and for waterproof coatings and floor coverings, do not drip when applied thickly to vertical wall surfaces or rising surfaces. Requires good spatula cutting property, and sealing material does not sag when applied to wide vertical joints or ceiling joints (does not slump), and requires a material with more thixotropic properties while maintaining workability. Has been done. Colloidal silica and fatty acid surface-treated calcium carbonate which have been generally used conventionally have a problem that workability is deteriorated when the compounding amount is increased to enhance thixotropic properties, and this requirement cannot be met.

The object of the present invention is to solve the above-mentioned problems of the prior art and to obtain a rubber-like elastic body which is hardened by moisture in the air and has excellent physical properties such as elongation and tensile adhesive strength, and is strong. to provide a manufacturing method of the curable assembly formed having a thixotropic.

[0005]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have conducted extensive studies and as a result, have found that a reaction product of an organic isocyanate and a compound having a primary and / or secondary amino group , a curable composition containing a crosslinkable silyl group-containing resin by a specific method, found that that can revealed emitting extremely excellent physical properties reinforcing effect and thixotropic effect, we have reached the present invention.

That is, the present invention relates to an organic isocyanate.
And a compound having a primary and / or secondary amino group
A hard resin containing a reaction product and a crosslinkable silyl group-containing resin.
A method for producing a volatile composition, comprising a crosslinkable silyl group-containing resin
In the presence of fat, organic isocyanates and primary and / or
Reacting with a compound having a secondary amino group,
It is the characteristic manufacturing method .

The present invention also relates to an organic isocyanate and a first
With a compound having a secondary and / or secondary amino group
Containing a compound, a crosslinkable silyl group-containing resin, and an additive
A method for producing a curable composition, comprising a crosslinkable silyl group.
With organic isocyanates in the presence of resin with primary and / or
Reacts with a compound having a secondary amino group, then
The above-mentioned production, characterized in that an additive is mixed therein.
Is the way .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The crosslinkable silyl group-containing resin in the present invention forms a siloxane bond by reacting with moisture (humidity) or water in the atmosphere to crosslink to form a rubber-like cured product. It is the resin contained above. Examples of such crosslinkable silyl group-containing resin include, for example, JP-A-52-7.
3998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043, and JP-A-63-1.
12642, JP-A-3-79627, JP-A-4-283259, JP-A-5-70531, JP-A-5-287186, and JP-A-11-80.
571, JP-A-11-116763, and JP-A-11-130931 may be mentioned. As the crosslinkable silyl group-containing resin in the present invention, specifically, a polyoxyalkylene-based polymer containing one or more crosslinkable silyl groups in the molecule and each main chain of which may contain an organosiloxane. Polymers, vinyl-modified polyoxyalkylene polymers, polyurethane polymers, vinyl polymers, polyester polymers, polycarbonate polymers, acrylic ester polymers, methacrylic acid ester polymers, polyolefin polymers , Copolymers thereof, and mixtures thereof. Further, a polyorganosiloxane polymer containing a crosslinkable silyl group, which is generally called RTV (room temperature vulcanizing) silicone rubber, can also be used. The crosslinkable silyl group, from the viewpoint of the curability of the curable composition and the physical properties after curing,
It is preferably contained in the molecule in an amount of 1 to 5. Further, the crosslinkable silyl group is preferably one represented by the following general formula, which is easy to crosslink and easy to produce.

[0009]

[Chemical 1] (In the formula, R is a hydrocarbon group, and is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 2 carbon atoms.
An aralkyl group of 0 is preferable, and a methyl group is most preferable. The reactive group represented by X is a halogen atom, a hydrogen atom,
A group selected from 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,
When X is plural, X may be the same group or different groups. Of these, X is preferably an alkoxy group, and most preferably a methoxy group or an ethoxy group. a is an integer of 0, 1 or 2, and 0 or 1 is the most preferable. )

The number average molecular weight of the crosslinkable silyl group-containing resin is 500 or more, particularly 1,000 to 30,000 and the molecular weight distribution is narrow, but the viscosity before curing is low, so that it is easy to handle and the tensile adhesive strength after curing. The rubber elastic properties such as elongation are suitable.

The crosslinkable silyl group-containing resin is crosslinked with (a) a crosslinkable silyl group-containing polyoxyalkylene resin and (b) a hydroxyl group-containing polyoxyalkylene polymer from the viewpoint of physical properties such as tensile adhesion strength after curing. Crosslinkable silyl group-containing resin obtained by reacting a reactive silyl group-containing isocyanate compound, (c) crosslinkable obtained by reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound, and an organic monoisocyanate Crosslinkable silyl group-containing resin, (d) crosslinkable silyl group-containing resin obtained by reacting a hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer with a crosslinkable silyl group-containing isocyanate compound, and (e) Hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer and crosslinkable silyl group-containing isocyanate Is preferably one or a mixture of any two or more selected from the group consisting of crosslinked silyl group-containing resin obtained by reacting a sulfonate compound and an organic monoisocyanate.

Specific examples of the crosslinkable silyl group-containing polyoxyalkylene resin (a) include crosslinkable silyl group-containing polyoxypropylene resin, crosslinkable silyl group-containing polyoxyethylene resin, and crosslinkable silyl group-containing polyoxyethylene resin. Examples thereof include (oxypropylene) -poly (oxyethylene) random copolymer resin or block copolymer resin, crosslinkable silyl group-containing polyoxytetramethylene resin, or a mixture thereof. Of these, the crosslinkable silyl group-containing polyoxypropylene resin is most preferable.

Crosslinkable silyl group-containing resin (b), (d)
Specifically, a hydroxyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing isocyanate compound, or a hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer and a crosslinkable silyl group-containing isocyanate compound. At an isocyanate group / hydroxyl group equivalent ratio of 0.
It is preferably 1 or more / 1.0, more preferably 0.5 to 1.5 / 1.0, particularly preferably 0.7 to 1.0 / 1.0. When the equivalent ratio of isocyanate group / hydroxyl group is less than 0.1 / 1.0, the crosslinkable silyl group-containing resin has few crosslinking groups and many hydroxyl groups, so that the physical properties of the cured product are not well expressed.

Crosslinkable silyl group-containing resin (c), (e)
Specifically, each of the isocyanate groups of the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate with respect to the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer, or the hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic group It can be obtained by reacting the crosslinkable silyl group-containing isocyanate compound and the respective isocyanate groups of the organic monoisocyanate with the hydroxyl groups of the polymer sequentially or simultaneously. When reacted sequentially, to the hydroxyl group-containing polyoxyalkylene polymer, or to the hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer, which is the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate first Although it may be reacted, it is preferable to first react the isocyanate compound containing a crosslinkable silyl group, and then to react the organic monoisocyanate. Crosslinkable silyl group-containing isocyanate compound for hydroxyl group of hydroxyl group-containing polyoxyalkylene polymer or silyl group-containing isocyanate compound for hydroxyl group of hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer The isocyanate group of is reacted at an equivalence ratio that leaves some hydroxyl groups to introduce a crosslinkable silyl group into the resin, and the isocyanate groups of the organic monoisocyanate are reacted with some or all of the remaining hydroxyl groups to cure with water. By adopting a structure in which a hydrophobic organic group having no property is introduced, rubber elasticity such as elongation after curing can be freely adjusted. Specifically, a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate, or a hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer and a crosslinkable silyl group-containing isocyanate The compound and the organic monoisocyanate have an isocyanate group / hydroxyl group equivalent ratio of 0.1 or more / 1.
0, more preferably 0.5 to 1.5 / 1.0, especially 0.7 to 1.
It is preferable to react in the range of 0 / 1.0. When the equivalent ratio of isocyanate group / hydroxyl group is less than 0.1 / 1.0, the crosslinkable silyl group-containing resin has few crosslinking groups and many hydroxyl groups, so that the physical properties of the cured product are not well expressed. When sequentially reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate, a hydroxyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing isocyanate compound, or a hydroxyl group-containing acryl When a system polymer and / or a hydroxyl group-containing methacrylic polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate are successively reacted, a hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer are crosslinked. With a hydrophilic silyl group-containing isocyanate compound, the equivalent ratio of isocyanate group / hydroxyl group is 0.05 to 0.9 / 1.0, and further 0.3 to
The reaction product and the organic monoisocyanate are allowed to react in a range of 0.9 / 1.0, and the equivalent ratio of isocyanate group / hydroxyl group is 0.1 or more in total of the crosslinkable silyl group-containing isocyanate compound. /1.0, and even 0.5
It is preferable to react in a range of from 1.5 to 1.0, particularly from 0.7 to 1.0 / 1.0.

The hydroxyl group-containing polyoxyalkylene polymer for producing the crosslinkable silyl group-containing resins (b) and (c) is a polymer obtained by ring-opening addition polymerization of alkylene oxide, or an alkylene oxide as an initiator. Examples thereof include polymers obtained by cycloaddition polymerization. As the initiator, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,
4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, low molecular weight alcohols such as sucrose, polyhydric phenols such as bisphenol A, low molecular weight polyamines such as ethylenediamine, diethanolamine, etc. Examples thereof include low molecular weight amino alcohols, or a mixture of two or more thereof. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture of two or more thereof. That is, the hydroxyl group-containing polyoxyalkylene polymer is a polyoxyalkylene polymer having one or more hydroxyl groups in the molecule, and specifically, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetraethylene. Mention may be made of methylene ether glycol, poly (oxyethylene) -poly (oxypropylene) -glycol, poly (oxyethylene) -poly (oxybutylene) -glycol, of which polyoxypropylene glycol is particularly preferred.
Further, these various polyols and conventionally known polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are reacted in excess of hydroxyl groups with respect to isocyanate groups, and a polymer having a hydroxyl group at the molecular end is also available. Can be mentioned. These may be used alone or in combination of two or more. The hydroxyl group-containing polyoxyalkylene polymer has a number average molecular weight of 1,000 to 30,000, and more preferably 8,000 to 8,000, from the viewpoint of high elongation of the cured product.
It is preferably 30,000, and the average number of hydroxyl groups per molecule is preferably from 1 to 8, particularly preferably from 2 to 4, and the total degree of unsaturation is 0.07 (meq / g) or less, particularly 0. Those having a narrow molecular weight distribution of 04 (meq / g) or less are preferable.

Crosslinkable silyl group-containing resins (b), (c),
The crosslinkable silyl group-containing isocyanate compound for producing (d) and (e) may contain at least one or more isocyanate group and at least one or more crosslinkable silyl group in the molecule. Is preferably one represented by the above general formula, which is easy to produce and easy to crosslink. As the crosslinkable silyl group-containing isocyanate compound, specifically, 3
-Isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylisopropoxysilane, isocyanatetrimethoxysilane, diisocyanatedimethoxysilane, etc. These may be used alone or in admixture of two or more.

The organic monoisocyanate for producing the crosslinkable silyl group-containing resins (c) and (e) may contain one isocyanate group in the molecule, but does not contain the crosslinkable silyl group. That is, the organic group other than the isocyanate group of the organic monoisocyanate is preferably a hydrophobic organic group containing no moisture-curable functional group such as moisture. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate and n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate. Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-diisopropyl monoisocyanate, p-
Aromatic monoisocyanates such as toluenesulfonyl monoisocyanate and p-benzyloxyphenyl monoisocyanate, as well as 2-methacryloyloxyethyl isocyanate and the like. Of these, aliphatic monoisocyanates are preferred. These can be used alone or in combination of two or more.

The hydroxyl group-containing acrylic polymer and / or hydroxyl group-containing methacrylic polymer for producing the crosslinkable silyl group-containing resin (d) or (e) is a hydroxyl group-containing acrylic monomer and / or hydroxyl group-containing acrylic polymer. In the presence or absence of a polymerization initiator, an ethylenically unsaturated compound containing at least a methacrylic monomer, and in the presence or absence of a solvent, known radical polymerization such as batch-type or continuous polymerization. Depending on the method, those obtained by a high-temperature continuous polymerization reaction at 150 to 350 ° C. are preferable because the polymer has a narrow molecular weight distribution and a low viscosity. The polymer may be obtained by polymerizing each of a hydroxyl group-containing acrylic monomer and a hydroxyl group-containing methacrylic monomer, or a polymer obtained by copolymerizing two or more of these. Alternatively, it may be obtained by copolymerizing one or more of each of these with an ethylenically unsaturated compound other than these. Among these, the hydroxyl group-containing acrylic monomer is easy to control the hydroxyl group content of the hydroxyl group-containing acrylic polymer and / or the hydroxyl group-containing methacrylic polymer, and the physical properties of the cured resin can be easily selected. A polymer obtained by copolymerizing one or more kinds of hydroxyl group-containing methacrylic monomers and one or more kinds of ethylenically unsaturated compounds other than these is preferable. At the time of this copolymerization, one type or two or more types of a hydroxyl group-containing acrylic monomer and a hydroxyl group-containing methacrylic monomer are contained so that the average number of hydroxyl groups per copolymer molecule is 1 to 20. It is preferable to use it so that it contains 1 to 10, more preferably 2 to 6 pieces. When the average number of hydroxyl functional groups exceeds 20, the physical properties after curing become too hard and the rubber-like elasticity is lost. Among them, the number average molecular weight is 1,000 to 30,000.
0, further 2,000 to 20,000, Tg is 0 ° C. or lower,
Especially, the viscosity at -20 ° C or lower, 25 ° C is 100,000.
A hydroxyl group-containing acrylic polymer and / or a hydroxyl group-containing methacrylic polymer of 0 mPa · s or less, particularly 50,000 mPa · s or less are preferable. Number average molecular weight 50,000
0, Tg 0 ° C, viscosity at 25 ° C 100,000 mP
If it exceeds a · s, the workability of the curable composition will deteriorate. As the hydroxyl group-containing acrylic monomer and the hydroxyl group-containing methacrylic monomer, good reactivity with the isocyanate group of the crosslinkable silyl group-containing isocyanate compound, and from the low viscosity of the resulting crosslinkable silyl group-containing resin An alcoholic hydroxyl group-containing acrylic monomer and an alcoholic hydroxyl group-containing methacrylic monomer are preferable, and specific examples thereof include hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxy. Hydroxyalkyl methacrylates such as propyl methacrylate and hydroxybutyl methacrylate, pentaerythritol triacrylate, glycerin monoacrylate, pentaerythritol diacrylate monostearate. Rate, dipentaerythritol pentaacrylate, ditrimethylolpropane triacrylate, polypropylene glycol monoacrylate and other polyhydric alcohol mono- or hydroxyl group residual polyacrylates, pentaerythritol trimethacrylate, glycerin monomethacrylate, pentaerythritol dimethacrylate monostearate, diester Pentaerythritol pentamethacrylate, ditrimethylolpropane trimethacrylate, polyglycols such as polypropylene glycol monomethacrylate mono- or hydroxyl group residual polymethacrylates, adducts of epoxide and acrylic acid such as adducts of cyclohexene oxide and acrylic acid, cyclohexene Of epoxides such as adducts of oxides and methacrylic acid with methacrylic acid Such as the addition thereof. Examples of the other ethylenically unsaturated compound include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinyl. Benzene, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, benzyl acrylate,
Glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, ethoxylated phenol acrylate, ethoxylated paracumylphenol acrylate,
Ethoxylated nonylphenol acrylate, propoxylated nonylphenol acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxylated bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate , Polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, polyurethane diacrylate, acrylic acid dimer, polyester polyacrylate, 1,6-
Hexanediol diacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone diacrylate, zinc diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin Triacrylate, ethoxylated pentae Thylitol tetraacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 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 methacrylate, trimethylolpropane trimethacrylate, etc. may be mentioned. Among these, as the ethylenically unsaturated compound, from the viewpoint of weather resistance and properties after curing, etc., an acrylic ester compound monomer, a methacrylic ester compound monomer, acrylamide, methacrylamide, acrylonitrile, and other acrylic compounds. Compounds and / or methacrylic compounds are preferable, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid. 2-Ethylhexyl is more preferred.

The organic isocyanate in the present invention is a compound having one or more isocyanate groups in the molecule and does not contain a crosslinkable silyl group. Specifically, for example, in addition to the organic monoisocyanate for producing the above-mentioned crosslinkable silyl group-containing resins (c) and (e), phenylene diisocyanate, diphenyl diisocyanate,
Naphthalene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, aromatic diisocyanate such as diphenyl ether diisocyanate, araliphatic diisocyanate such as xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, aliphatic diisocyanate such as butylene diisocyanate, cyclohexane diisocyanate, Examples thereof include organic diisocyanates such as alicyclic diisocyanates such as methylenebis (cyclohexylisocyanate) and isophorone diisocyanate. Further, so-called modified isocyanate such as adduct modified product, burette modified product, isocyanurate modified product, uretonimine modified product, uretdione modified product, carbodiimide modified product and the like can also be used. Furthermore, polyisocyanates called so-called polymeric compounds such as polyphenylene polymethylene polyisocyanate and crude toluene polyisocyanate can also be used. Further, an isocyanate group-containing compound obtained by reacting the organic isocyanate with a low molecular weight polyol such as propylene glycol, trimethylolpropane, or glycerin in excess of an isocyanate group with respect to an active hydrogen group can also be used. These can be used alone or in admixture of two or more. Of these, aromatic polyisocyanates are preferred, and polyphenylene polymethylene polyisocyanates are more preferred.

The compound having a primary and / or secondary amino group in the present invention includes primary and / or secondary
Examples thereof include monoamines or polyamines having a primary amino group, and no crosslinkable silyl group is contained in the molecule. Examples of primary amines include butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, and 3-methoxypropylamine as monoamines.
Examples thereof include tetradecylamine, pentadecylamine, cetylamine, stearylamine, oleylamine, trimethylcyclohexylamine, benzylamine and aniline. As diamines, 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-
Diaminoundecane, 1,12-diaminododecane,
1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,1
6-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-
Diamino nonadecane, 1,20-diamino eicosane,
1,21-Diaminogenticosan, 1,22-Diaminodocosane, 1,23-Diaminotricosane, 1,24
-Diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, Examples include diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, polyoxypropylenediamine, and the like, and triamine includes tri (methylamino) hexane and the like. Examples of the secondary amine include diethylamine, dipropylamine, diisopropylamine, dibutylamine, dihexylamine, di-2-ethylhexylamine, diphenylamine, dilaurylamine, distearylamine, methyllaurylamine, and other monoamines, N, N '. -Dilaurylpropyldiamine, N,
N'-Distearyl butyl diamine, N-butyl-N '
Examples include diamines such as -laurylethyldiamine, N-butyl-N'-laurylpropyldiamine and N-lauryl-N'-stearylbutyldiamine.
Examples of other amines include N-lauryl propylene diamine and N-stearyl propylene diamine. Examples of the polyamine having a primary amino group and a secondary amino group include diethylenetriamine, triethylenetetramine, methylaminopropylamine and the like. These may be used alone or in admixture of two or more. Of these, primary amines are preferable, and primary monoamines are particularly preferable because of their thixotropic effect.

The organic isocyanate and the primary and / or
Or, with a compound having a secondary amino group, the equivalent ratio of isocyanate group / active hydrogen group is 0.01 / 1 to 10/1,
Furthermore, it is preferable to react in the range of 0.1 / 1 to 2/1, particularly 0.1 / 1 to 1/1. If the equivalent ratio of isocyanate group / active hydrogen group is less than 0.01 / 1, the thixotropic effect is too small, and if it exceeds 10/1, a large amount of unreacted isocyanate groups remain, and adverse effects such as foaming occur. come.

The reaction product of the organic isocyanate and the compound having a primary and / or secondary amino group is 0.1 to 30 with respect to 100 parts by weight of the crosslinkable silyl group-containing resin.
It is preferable to add 0 parts by weight, particularly 1 to 100 parts by weight. When the content is less than 0.1, the thixotropic effect is too small, and when it exceeds 300 parts by weight, workability is deteriorated.

In the present invention, by reacting an organic isocyanate with a compound having a primary and / or secondary amino group in the presence of a resin containing a crosslinkable silyl group .
Therefore, the reaction product of the organic isocyanate and the compound having a primary and / or secondary amino group is finely and uniformly dispersed in the crosslinkable silyl group-containing resin, resulting in physical properties such as elongation and tensile adhesive strength. The effect of improving
Yes.

The additives in the present invention include a crosslinking catalyst, an antioxidant, an ultraviolet absorber, a reinforcing agent, a bulking filler, a coupling agent, a thixotropic agent, a storage stability improving agent (dehydrating agent),
Colorants and the like can be mentioned.

The cross-linking catalyst is a catalyst for promoting cross-linking (curing) of the cross-linkable silyl group-containing resin, and specific examples thereof include organic metal compounds and amines. Among them, the cross-linking rate is excellent. Preferred are organic tin compounds. This organotin compound is specifically stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin. Among them, dilaurate and dioctyltin diversate are preferred, and among them, dibutyltin diacetylacetonate is most preferable because it is a liquid having a high crosslinking rate and relatively low toxicity and brilliance. The crosslinking catalyst is used in an amount of 0.01 to 10 parts by weight, particularly 0.05 to 10 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing resin, from the viewpoints of crosslinking speed, physical properties of the cured product, and the like.
It is preferable to add 1 part by weight.

Antioxidants and ultraviolet absorbers can be used for preventing oxidation, photodegradation and heat deterioration of the cured resin, and further improving not only weather resistance but also heat resistance. Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. As the hindered amine-based antioxidant, for example,
[Bis (2,2,6,6-tetramethyl-1decanedioate-1
(Octyloxy) -4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4
-Hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4 -Benzoyloxy-2,2,6,6-tetramethylpiperidine. Further, each compound of the ADEKA STAB series manufactured by Asahi Denka Kogyo KK can be mentioned. Examples of the hindered phenolic antioxidant include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3-.
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid 3,5-
Bis (1,1-dimethylethyl) -4-hydroxy C7
-C9 side chain alkyl ester, 2,4-dimethyl-6-
(1-methylpentadecyl) phenol is mentioned.
Examples of the ultraviolet absorber include 2- (3,5-di-t
benzotriazole-based UV absorbers such as ert-butyl-2-hydroxyphenyl) benzotriazole, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-[(hexyl) oxy] -phenol and other triazine-based UV absorbers, octabenzone and other benzophenone-based UV absorbers, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl Examples thereof include benzoate-based UV absorbers such as 4-hydroxybenzoate.

Reinforcing agents, extending fillers, coupling agents, thixotropic agents, storage stability improving agents (dehydrating agents), coloring agents and the like can be used for improving adhesiveness, reinforcing, preventing sagging and the like. Examples of the reinforcing / extending filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, diatomaceous earth, fatty acid-treated calcium carbonate (also having a thixotropic effect), and those having a particle size of 1 to 100 μm. Is preferred. Examples of the coupling agent include silane-based, aluminum-based, and zircoaluminate-based coupling agents. Of these, silane-based coupling agents are preferable because of their excellent adhesiveness. As the silane coupling agent, specifically, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane,
Examples thereof include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. In the present invention, since the reaction product of the organic isocyanate and the compound having a primary and / or secondary amino group has a large thixotropic effect, other thixotropic agents may not be used. It can also be used as a supplement. 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. Examples of the storage stability improver include low molecular weight crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane and calcium oxide, which react with water present in the composition. Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

In the curable composition of the present invention, each of the additive components may be used alone or in combination of two or more.

In the curable composition of the present invention, if necessary, a conventionally known organic compound such as an aliphatic solvent such as n-hexane, an alicyclic solvent such as cyclohexane, an aromatic solvent such as toluene or xylene, etc. Any solvent that does not react with the components of the curable composition in a solvent can be used alone or in combination of two or more. The type and the amount used may be appropriately determined according to the application of the curable composition.

The curable composition of the present invention is preferably used as a one-part moisture curable composition from the viewpoint of workability, but the curable composition of the present invention is used as a main component and a curing agent such as water is mixed. It can also be used as a two-component curing type for curing.

[0031]

EXAMPLES The present invention will now be described in more detail by way of examples. Here, an elastic adhesive composition is shown as an example of the curable composition, but the curable composition is not limited thereto.

[0032]Synthesis example 1 Heating with stirrer, thermometer, nitrogen seal tube and cooler
In the reaction vessel, polyoxypropylene glycol (number average
Molecular weight 16,000, total satiety 0.02 meq / g, Asahi
Glass PML-4016) 800 g (OH equivalent:
0.1) Charge and stir 3-isocyanate while stirring
Piltriethoxysilane (KBE-9 manufactured by Shin-Etsu Chemical Co., Ltd.
007, measured isocyanate group content by titration 16.
4% by weight) 20.5 g (NCO equivalent: 0.08) (R value
(NCO equivalent / OH equivalent) = 0.8) and dibutyltin dill
After adding 0.82 g of urate, warm it to 1 at 80 ° C.
Stir for 0 minutes to measure the isocyanate group content by titration.
0.00 wt% and FTIR isocyanate
After confirming the disappearance of the peak of the base group, the mixture was cooled. Then in this
In addition, 5.9 g of octadecyl monoisocyanate (NCO
Equivalent: 0.02) (R value (NCO equivalent / OH equivalent) =
0.2) was added, the mixture was heated again and stirred at 80 ° C. for 20 minutes.
Disappearance of peak of isocyanate group by FTIR
Was confirmed, and the reaction was terminated by cooling to room temperature. Obtained
Polyethoxypropylene-containing triethoxysilyl group
The theory of retan resin is semi-transparent at room temperature, measured by titration
Isocyanate group content 0.00 wt%, viscosity 16,0
It was a liquid of 00 mPa · s / 25 ° C. This resin is N
It is called U-1.

[0033]Synthesis example 2 Add polyoxypropylene to the same warm reaction vessel as in Synthesis Example 1.
Glycol (number average molecular weight 16,000, total satiety)
0.02 meq / g, PML-4016 manufactured by Asahi Glass Co., Ltd.
Charge 800 g (OH equivalent: 0.1) and stir 3
-Isocyanate propyltriethoxysilane (Shin-Etsu
Gaku Kogyo's KBE-9007, Isometrically measured by titration
Nate group content 16.4% by weight) 20.5 g (NCO equivalent)
Amount: 0.08) (R value (NCO equivalent / OH equivalent) = 0.
8) and 0.82 g of dibutyltin dilaurate were added
Then, heat and stir at 80 ° C for 10 minutes, and then titrate
Measured isocyanate group content 0.00 wt%, FT
Confirm the disappearance of the peak of the isocyanate group by IR,
The reaction was terminated by cooling to room temperature. Obtained triet
Xysilyl-containing polyoxypropylene-urethane resin
The fat is a semi-transparent theory at room temperature, and isocyante actually measured by titration.
Content of 0.001 wt%, viscosity of 15,400 mPas
-It was a liquid at s / 25 ° C. This resin is called NU-2
To do.

[0034]Synthesis example 3 A hydroxyl group-containing acrylic resin was placed in a warm reaction vessel similar to that used in Synthesis Example 1.
-Based polymer (number average molecular weight 13,000, hydroxyl value 20.
5mgKOH / g, average number of hydroxyl groups 4.8, Toagosei Co., Ltd.
733.7 g (OH equivalent) manufactured by Gaku Kogyo Co., Ltd.
Amount: 0.27) 3-isocyanate with charging and stirring
Topropyltriethoxysilane (KB manufactured by Shin-Etsu Chemical Co., Ltd.
E-9007, Measured isocyanate group content by titration
16.4% by weight) 33.2 g (NCO equivalent: 0.13)
(R value (NCO equivalent / OH equivalent) = 0.5) and dibutyl
After adding 0.8 g of tin dilaurate, heat to 70-
Stir at 80 ° C for 1 hour and use FTIR to obtain isocyanate.
After confirming the disappearance of the peak of the acetate group, the mixture was cooled to room temperature. Next
In this, octadecyl monoisocyanate 39.
8 g (NCO equivalent: 0.135) (R value (NCO equivalent /
OH equivalent) = 0.5) was added, and the mixture was reheated to 1 at 80 ° C.
After stirring for an hour, FTIR is performed to measure the isocyanate group
After confirming the disappearance of the
It was Obtained triethoxysilyl group-containing acrylic-urea
Tan resin is a theory of semi-transparency at room temperature,
Socyanate group content 0.00% by weight, viscosity 16,20
It was a liquid of 0 mPa · s / 25 ° C. This resin is NU
-3.

[0035]Synthesis example 4 A hydroxyl group-containing acrylic resin was placed in a warm reaction vessel similar to that used in Synthesis Example 1.
-Based polymer (number average molecular weight 13,000, hydroxyl value 20.
5mgKOH / g, average number of hydroxyl groups 4.8, Toagosei Co., Ltd.
733.7 g (OH equivalent) manufactured by Gaku Kogyo Co., Ltd.
Amount: 0.27) 3-isocyanate with charging and stirring
Topropyltriethoxysilane (KB manufactured by Shin-Etsu Chemical Co., Ltd.
E-9007, Measured isocyanate group content by titration
16.4% by weight) 33.2 g (NCO equivalent: 0.13)
(R value (NCO equivalent / OH equivalent) = 0.5) and dibutyl
After adding 0.8 g of tin dilaurate, heat to 70-
Stir at 80 ° C for 1 hour and use FTIR to obtain isocyanate.
After confirming the disappearance of the peak of the acetate group, cool to room temperature and react
Ended. The obtained triethoxysilyl group-containing ac
Ril-urethane resin is semi-transparent at room temperature
Measured by isocyanate group content 0.00 wt%, viscosity
The liquid was 15,500 mPa · s / 25 ° C. this
The resin is called NU-4.

[0036]Example 1 In a kneading container equipped with a heating and cooling device,
Lioxypropylene resin (number average molecular weight 20,000,
Asahi Glass ES-S3630) 800g and polyphenyle
Polymethylene polyisocyanate (Sumitomo Bayer Ure
67.8 g of Sumidule 44V-20 manufactured by Tan Co., Ltd. (NC
O equivalent: 0.5) was added, stirred, mixed, and cooled.
Meanwhile, oleylamine (Pharmine O manufactured by Kao) 1
32 g (active hydrogen group equivalent: 1.0) (NCO equivalent / activity
Hydrogen group equivalent = 0.5 / 1) was charged and stirred for 1 hour,
Mixed. At first, the contents were fluid, but
It was confirmed that it became a paste that was not fluid
It was The content of isocyanate group measured by titration was 0.
It is 0% by weight, and the isocyanate group is further determined by FTIR.
The disappearance of the peak was confirmed. Then dibutyltin diacetate
Chillacetonate (Neostan U-22 manufactured by Nitto Kasei)
0) Charge 0.8 g and stir until the contents are uniform,
After mixing, defoaming under reduced pressure to prepare an elastic adhesive composition.
It was

[0037]Example 2 In Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) in place of the trieto obtained in Synthesis Example 1.
Xysilyl-containing polyoxypropylene-urethane resin
An elastic adhesive assembly was prepared in the same manner except that the fat NU-1 was used.
The product was prepared.

[0038]Example 3 In Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) in place of the trieto obtained in Synthesis Example 2
Xysilyl-containing polyoxypropylene-urethane resin
In the same manner except that the fat NU-2 was used, an elastic adhesive set
The product was prepared.

[0039]Example 4 In Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) was obtained in Synthesis Example 1 instead of 800 g.
Polyoxypropylene containing triethoxysilyl group-urea
Tanner resin NU-1 480 g and the Trier obtained in Synthesis Example 3
Toxysilyl group-containing acrylic-urethane resin NU-3
  An elastic adhesive set was made in the same manner except that 320 g was used.
The product was prepared.

[0040]Example 5 In Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) was obtained in Synthesis Example 1 instead of 800 g.
Polyoxypropylene containing triethoxysilyl group-urea
Tanner resin NU-1 (480 g) and the trie obtained in Synthesis Example 4
Toxysilyl group-containing acrylic-urethane resin NU-4
  An elastic adhesive set was made in the same manner except that 320 g was used.
The product was prepared.

[0041]Comparative Example 1 In a kneading container equipped with a heating and cooling device,
Lioxypropylene resin (number average molecular weight 20,000,
Asahi Glass Co., Ltd. ES-S3630) 800 g and dibutyl tin di
Acetylacetonate (Neostan U-2 manufactured by Nitto Kasei)
20) Charge 0.8g and stir until the contents are uniform.
Stir and mix, then defoam under reduced pressure to prepare an elastic adhesive composition
did.

[0042]Comparative example 2 In Comparative Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) in place of the trieto obtained in Synthesis Example 1.
Xysilyl-containing polyoxypropylene-urethane resin
An elastic adhesive assembly was prepared in the same manner except that the fat NU-1 was used.
The organism was prepared.

[0043]Comparative Example 3 In a kneading container equipped with a heating and cooling device,
Lioxypropylene resin (number average molecular weight 20,000,
800 g of ES-S3630 manufactured by Asahi Glass Co., Ltd., fatty acid (table
Surface treated calcium carbonate (Calfa manufactured by Maruo Calcium Co., Ltd.
In 200M) 200g is charged to make the contents uniform
And stirred until mixed. Then depressurized dehydration at 110 ℃ for 1 hour.
And after cooling, dibutyltin diacetylacetonate
(Nitto Kasei Neostan U-220) 0.8g
Mix and stir until the contents are uniform, and then depressurize.
Foamed to prepare an elastic adhesive composition.

[0044]Comparative Example 4 In Comparative Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) in place of the trieto obtained in Synthesis Example 2
Xysilyl-containing polyoxypropylene-urethane resin
In the same manner except that the fat NU-2 was used, an elastic adhesive set
The product was prepared.

[0045]Comparative Example 5 In Comparative Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) was obtained in Synthesis Example 1 instead of 800 g.
Polyoxypropylene containing triethoxysilyl group-urea
Tanner resin NU-1 480 g and the Trier obtained in Synthesis Example 3
Toxysilyl group-containing acrylic-urethane resin NU-3
  An elastic adhesive set was made in the same manner except that 320 g was used.
The product was prepared.

[0046]Comparative Example 6 In Comparative Example 1, a crosslinkable silyl group-containing polyoxypro
Pyrene resin (number average molecular weight 20,000, E manufactured by Asahi Glass Co., Ltd.
S-S3630) was obtained in Synthesis Example 1 instead of 800 g.
Polyoxypropylene containing triethoxysilyl group-urea
Tanner resin NU-1 (480 g) and the trie obtained in Synthesis Example 4
Toxysilyl group-containing acrylic-urethane resin NU-4
  An elastic adhesive set was made in the same manner except that 320 g was used.
The product was prepared.

[Performance Test] The following tests were conducted using the elastic adhesive compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6. (1) Slump (longitudinal) was measured in accordance with "4.1 Slump test" of JIS A1439: 1997 "Testing method for building sealing material" (measurement temperature 23 ° C). (2) Tensile adhesion strength According to "4.21 Tensile Adhesion Test" of JIS A1439: 1997 "Testing Method for Sealing Materials for Buildings", a tensile test was performed on test specimens after curing. The test body was prepared by treating the slate with a primer (OP2531, manufactured by Auto Kagaku Kogyo Co., Ltd.), casting and curing the elastic adhesive composition. (3) Shift resistance According to JIS A5548: 1993 “Adhesive for ceramic tiles”, “5.4.5 Shift resistance test method”,
The shift length was measured using a 100 mm square tile with a thickness of 10 mm (test temperature 23 ° C.). The results and the composition of the elastic adhesive composition are summarized in Tables 1 and 2.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

Industrial Applicability As described above, according to the present invention, a moisture-curable type which is easy to manufacture and is cured by moisture in the atmosphere to be a rubber-like elastic body having excellent physical properties such as elongation and tensile adhesive strength. It has become possible to provide a curable composition.
That is, the curable composition obtained by the production method of the present invention has a urea bond-containing compound obtained by reacting an organic isocyanate and a compound having a primary and / or secondary amino group in a crosslinkable silyl group-containing resin. Dispersed evenly, thixotropic (slump) as well as elongation and tensile adhesive strength (Tma
x, Emax) could be improved. for that reason,
It is not necessary to use a reinforcing filler in the curable composition obtained by the production method of the present invention, or the amount used can be significantly reduced. That is, the production method of the present invention
The curable composition obtained by the method has a large elongation and excellent displacement followability, and also has a high tensile adhesive strength, so that the rubber elasticity is high, and when it is adhered to a wall surface such as a heavy tile, it does not shake easily. Degeneration can be expressed. Therefore, it is particularly suitable for elastic paints (elastic adhesives, waterproof coatings, coated flooring materials, etc.) for buildings, civil engineering, automobiles, etc., putty materials, and sealing materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masato Kobayashi, inventor Masato Kobayashi 2044, Kaminaeda, Chiyoda-cho, Shinji-gun, Ibaraki Auto Chemical Industry Co., Ltd. Technical Research Laboratory (72) Yasuko Kinoshita 2044, Kaminaida-kichi, Chiyoda-cho, Shinji-gun, Ibaraki Address No. 6 Auto Chemical Industry Co., Ltd. Technical Research Laboratory (72) Inventor Mitsuru Aono 2044 Kaminayoshi, Chiyoda-cho, Shinji District, Ibaraki Prefecture No. 6 Auto Chemical Industrial Co., Ltd. Technical Research Laboratory (56) Reference JP-A-8-269342 ( JP, A) JP 9-3153 (JP, A) JP 8-134168 (JP, A) JP 2001-172513 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) C08L 1/00-101/16 C08G 18/00-18/87

Claims (4)

(57) [Claims] 1.Organic isocyanate and primary and / or
Crosslinking with a reaction product with a compound having a secondary amino group
Of Curable Composition Containing Resin with Hydrophilic Silyl Group
The law, In the presence of the crosslinkable silyl group-containing resin, organic isocyanate
And a compound having a primary and / or secondary amino group
The above-mentioned production method, characterized in that: 2.Organic isocyanate and primary and / or
Crosslinking with a reaction product with a compound having a secondary amino group
Curable composition containing a polymerizable silyl group-containing resin and an additive
A method of manufacturing a product, Organic isocyanate in the presence of a resin containing a crosslinkable silyl group
And a compound having a primary and / or secondary amino group
The reaction and then mixing the additives into it.
The manufacturing method as described above. 3. The crosslinkable silyl group-containing resin is (a)
Crosslinkable silyl group-containing polyoxyalkylene resin, (b)
Hydroxyl group-containing polyoxyalkylene polymer and crosslinkable silyl
A rack obtained by reacting with a group-containing isocyanate compound
Bridge-containing silyl group-containing resin, (c) hydroxyl group-containing polyoxya
Rukiren polymer and crosslinkable silyl group-containing isocyanate
Obtained by reacting compound with organic monoisocyanate
Crosslinkable silyl group-containing resin, (d) hydroxyl group-containing acrylic resin
Crosslinking with polymer and / or hydroxyl group-containing methacrylic polymer
Obtained by reacting with a silyl group-containing isocyanate compound
Crosslinkable silyl group-containing resin and (e) hydroxyl group-containing resin
Acrylic polymer and / or hydroxyl group-containing methacrylic polymer
Combined and crosslinkable silyl group-containing isocyanate compound and organic
Crosslinkable silicone obtained by reacting with monoisocyanate
1 or 2 or more selected from the group consisting of a group-containing resin
The method for producing the curable composition according to claim 1 or 2, wherein
Law . 4. The method according to claim 2, wherein the additive is a crosslinking catalyst.
The method for producing a curable composition according to item 1 .