JP2003064253A - Curable composition and sealant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an one-component moisture-curable type curable composition and a sealant composition of low viscosity that have remarkably excellent weather resistance especially, proper adhesion, superior heat resistance and excellent durability such as water resistance, and that is produced easily and has good workability with being a rubber-like elastomer of low modulus and of large elongation by hardening by moisture in the atmosphere. SOLUTION: This curable composition and sealant composition contain an isocyanate group containing urethane prepolymer and crosslinkable silyl group containing poly acrylic and/or methacrylic resins as curable components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a workability, an adhesive property, a workability, an adhesive property, which is cured by moisture in the atmosphere to form a rubber-like elastic body.
The present invention relates to a curable composition and a sealing material composition having excellent durability and the like.

[0002]

2. Description of the Related Art Polyurethane resin has been used as a moisture-curable resin component for curable compositions such as waterproof sealing materials for buildings, civil engineering and automobiles, adhesives and paints. It is widely used because of its excellent properties and adhesiveness.

[0003]

However, in recent years,
In the fields of buildings, civil engineering, automobiles, etc., there is a growing need for so-called ultra-long life, which maintains performance over a long period of time, and the adhesiveness to sealants, adhesives, paints, etc. Further, further improvement in durability such as heat resistance, water resistance and weather resistance is required. Polyurethane resin has an appropriate modulus after curing, has a large elongation and good rubber elasticity, is excellent in adhesiveness and water resistance, and is easy to manufacture,
Although it has the advantage of being relatively inexpensive, it has the disadvantage of poor weather resistance.

The object of the present invention is to solve the above-mentioned problems of the prior art, to make it easy to manufacture and to have good workability, and to obtain a rubber-like elasticity which is cured by moisture in the atmosphere and has a low modulus and a large elongation. By providing a low-viscosity one-component moisture-curable curable composition and a sealing material composition, which have a particularly good weather resistance, and which are excellent in durability such as adhesion, heat resistance, and water resistance. is there.

[0005]

In order to achieve the above object, the present invention is the following (1) to (7). (1) A curable composition comprising an isocyanate group-containing urethane prepolymer and a crosslinkable silyl group-containing polyacrylic and / or methacrylic resin as curing components.

(2) The isocyanate group-containing urethane prepolymer is obtained by reacting an organic polyisocyanate and a high molecular weight polyether polyol under the condition of excess isocyanate groups with respect to hydroxyl groups. Is a prepolymer,
The curable composition according to (1) above.

(3) The crosslinkable silyl group-containing polyacrylic and / or methacrylic resin is a resin obtained by reacting a polyacrylic and / or methacrylic polyol with a crosslinkable silyl group-containing isocyanate compound, The curable composition according to (1) or (2) above.

(4) The crosslinkable silyl group-containing polyacrylic and / or methacrylic resin is obtained by reacting a polyacrylic and / or methacrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and an organic monoisocyanate. (1) or (2), which is a resin
Curable composition.

(5) The curable composition according to any one of the above (1) to (4), which further contains an additive.

(6) The curability according to (4) above, wherein the additive is an antioxidant, an ultraviolet absorber, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent and / or a storage stability improver. Composition.

(7) Containing a urethane prepolymer containing an isocyanate group and a polyacrylic and / or methacrylic resin containing a crosslinkable silyl group as curing components,
A sealant composition comprising:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Isocyanate group-containing urethane prepolymer as a curing component in the present invention, an isocyanate group reacts with moisture (moisture) to form a urea bond and crosslink, and to cure, an organic polyisocyanate, a polymer polyol, In some cases, a compound obtained by reacting a chain extender with an active hydrogen (group) under an isocyanate group excess condition is preferable.

As the organic polyisocyanate, 4,
4'-diphenylmethane diisocyanate, 2,4'-
Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,
4'-diphenyl ether diisocyanate, 3,3 '
-Dimethyldiphenyl-4,4'-diisocyanate,
4,4'-diphenylpropane diisocyanate, 1,
Aroma such as 2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Aliphatic diisocyanates such as group diisocyanates, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, lysine diisocyanate methyl ester, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethyl xylene diisocyanate, etc. Aromatic aliphatic diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated Diphenylmethane diisocyanate, organic diisocyanates and alicyclic diisocyanates such as hydrogenated tetramethylxylylene diisocyanate are preferred. Further, so-called modified isocyanates such as adduct modified products, burette modified products, isocyanurate modified products, uretonimine modified products, uretdione modified products and carbodiimide modified products of these organic diisocyanates can also be used. Furthermore, polyisocyanates called so-called polymeric compounds such as polyphenylene polymethylene polyisocyanate and crude toluene polyisocyanate can also be used. These organic polyisocyanates can be used alone or in combination of two or more.

Examples of the polymer polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, animal and plant polyols, copolyols thereof, and the like, or a mixture of two or more thereof. Among these polymer polyols, polyether polyols are preferable because they are excellent in workability, adhesiveness, water resistance, weather resistance and the like.

Examples of polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid,
Hexahydroorthophthalic acid, naphthalenedicarboxylic acid, polycarboxylic acids such as trimellitic acid, acid esters,
Or one or more of acid anhydrides and ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3 -Methyl-1,5-
Pentanediol, neopentyl glycol, 1,8-
Octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide or propylene oxide adduct, trimethylolpropane, glycerin, pentaerythritol and other low molecular weight alcohols, Examples include polyester polyols or polyester amide polyols obtained by dehydration condensation reaction with one or more low molecular weight amines such as hexamethylene diamine, xylylenediamine, isophorone diamine, and low molecular weight amino alcohols such as monoethanolamine and diethanolamine. To be Further, for example, a lactone-based polyester polyol obtained by ring-opening polymerization of a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone using low molecular weight alcohols, low molecular weight amines or low molecular weight amino alcohols as an initiator. Is mentioned.

Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular weight alcohols and phosgene used in the synthesis of the above polyester polyol, or low molecular weight alcohols and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc. Those obtained by the transesterification reaction with

As the polyether polyol, for example, ethylene oxide, propylene oxide, tetrahydrofuran, etc. are initiated by using low molecular alcohols, low molecular amines, and low molecular amino alcohols used in the synthesis of the above-mentioned polyester polyol as an initiator. Examples thereof include ring-polymerized polyoxyethylene polyols, polyoxypropylene polyols, polytetramethylene ether polyols, polyether polyols obtained by copolymerizing these, and polyester ether polyols having the above-mentioned polyester polyols and polycarbonate polyols as initiators. Further, as a modifier for the urethane prepolymer containing an isocyanate group, a monoalcohol such as methyl alcohol, ethyl alcohol or propyl alcohol may be used as an initiator, and a polyoxyalkylene monool such as propylene oxide may be used.
Of these, polyoxypropylene polyol is particularly preferable.

Examples of the polyolefin polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene and hydroxyl group-containing chlorinated polyethylene.

As the acrylic polyol, for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and the like, a monomer and / or a hydroxyl group of an acrylic acid compound containing a hydroxyl group. A monomer of a methacrylic acid-based compound containing at least one of ethylenically unsaturated compounds other than these, in the presence or absence of a radical polymerization initiator, and in the presence or absence of a solvent. Examples thereof include those obtained by reacting by a known radical polymerization method such as formula polymerization or continuous polymerization.

Examples of animal and vegetable polyols include castor oil-based diols.

If it has an active hydrogen group,
For example, in addition to dimer acid type diol and hydrogenated dimer acid type diol, epoxy resin, polyamide resin, polyester resin, rosin resin, urea resin, melamine resin,
Resins such as phenol resin, coumarone resin and polyvinyl alcohol can also be used as the polymer polyol.

The number average molecular weight of these polymer polyols is 500 to 30,000, and particularly 1,000 to 20,000.
0 is preferred.

As the chain extender, the molecular weight of the low molecular weight alcohols, low molecular weight amines and low molecular weight amino alcohols used in the synthesis of the above polyester polyol is 5
Preferable examples are those of less than 00, or a mixture of two or more kinds thereof.

For the synthesis of the isocyanate group-containing urethane prepolymer in the present invention, zinc octenoate, etc.,
Metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron with organic acids such as octenoic acid and naphthenic acid, organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate, triethylenediamine, triethylamine A known urethanization catalyst such as an organic amine such as tri-n-butylamine or a salt thereof can be used. Of these, dibutyltin dilaurate is preferred. Further, a known organic solvent can also be used.

The isocyanate group-containing urethane prepolymer in the present invention can be synthesized by a batch charging reaction method or a multi-step charging reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. Isocyanate group consisting of isocyanate group of organic polyisocyanate and polymer polyol, and optionally hydroxyl group of chain extender /
The equivalent ratio of hydroxyl groups is preferably 1.1 to 5.0, more preferably 1.3 to 2.0. The isocyanate group-containing urethane prepolymer thus obtained has an isocyanate group content of preferably 0.1 to 15.0% by mass, particularly preferably 0.3 to 10.0% by mass, and most preferably 0.4 to It is 5.0 mass%. If the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability deteriorates. Further, since there are few crosslinking points in the resin, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, the molecular weight of the resin is too small and the rubber elasticity deteriorates.

The crosslinkable silyl group-containing polyacrylic and / or methacrylic resin (hereinafter, "acrylic and / or methacrylic" is referred to as (meth) acrylic resin) as a curing component in the present invention has a crosslinkable silyl group. Crosslinks by reacting with moisture (moisture), hydrolyzing to generate silanol groups, and then silanol groups are dehydrated and condensed,
It cures, and its compounding exerts an effect of remarkably improving weather resistance after curing. Preferably, for example, it can be obtained by reacting a poly (meth) acrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and optionally an organic monoisocyanate sequentially or simultaneously. More specifically, poly (meth)
Acrylic polyol and crosslinkable silyl group-containing isocyanate compound are reacted in an equivalent ratio of isocyanate group / hydroxyl group of 1 or more, and more preferably 1.0 to 1.5 / 1.0 to suitably produce. be able to. Also, first
The poly (meth) acrylic polyol and the crosslinkable silyl group-containing isocyanate compound are preferably added to the isocyanate group such that at least one hydroxyl group remains in the reaction product, more preferably substantially one hydroxyl group remains. Under the condition of excess hydroxyl groups, the equivalent ratio of isocyanate group / hydroxyl group is 0.
1-0.99 / 1.0, further 0.3-0.8 / 1.0
To produce a crosslinkable silyl group- and hydroxyl group-containing poly (meth) acrylic resin, and then the crosslinkable silyl group- and hydroxyl group-containing poly (meth) acrylic resin and an organic monoisocyanate, The isocyanate group / hydroxyl group equivalent ratio is 1 or more, and further 1.0 to 1.5 /
It can be suitably produced by reacting in the range of 1.0. In these reactions, the known urethanization catalysts mentioned in the synthesis of the isocyanate group-containing urethane prepolymer can be used. Of these, dibutyltin dilaurate is preferred. Further, a known organic solvent can also be used.

The poly (meth) acrylic polyol is an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer in the presence or absence of a polymerization initiator and in the presence of a solvent. In the absence,
By a known radical polymerization method such as batch type or continuous polymerization, preferably 150 to 350 ° C., more preferably 2
What is obtained by a high temperature continuous polymerization reaction at 10 to 250 ° C. is preferable because the molecular weight distribution of the reaction product is narrow and the viscosity is low. The poly (meth) acrylic polyol may be obtained by polymerizing a hydroxyl group-containing (meth) acrylic monomer alone, and further, it may be copolymerized with another ethylenically unsaturated compound. It may be obtained by Among these, the hydroxyl group-containing (meth) acrylic monomer and ethylene other than this are easy to control the hydroxyl group content of the poly (meth) acrylic polyol and easily select the physical properties of the cured resin. Those obtained by copolymerizing a polyunsaturated compound are preferable. During this copolymerization,
Hydroxyl group-containing (meth) acrylic monomer is added to poly (meth)
It is preferable to use it so that the average number of hydroxyl functional groups per molecule of acrylic polyol is 1.1 to 10.
Furthermore, it is preferable to use it so that 1.2 to 6, especially 1.5 to 3, may be contained. If the average number of hydroxyl functional groups exceeds 10, the physical properties after curing become too hard and the rubber-like elasticity is lost. Among them, the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 1,000 to 30,000, and further 1,000 to 15,
000, Tg is 0 ° C. or lower, further -70 to −20 ° C., particularly −70 to −30 ° C., viscosity at 25 ° C. is 100,000.
A poly (meth) acrylic polyol of 0 mPa · s or less, particularly 50,000 mPa · s or less is preferable. Number average molecular weight 30,000, Tg 0 ° C, viscosity at 25 ° C 1
If it exceeds 0.00000 mPa · s, the workability of the curable composition will be poor.

Examples of the hydroxyl group-containing (meth) acrylic monomer include crosslinkable silyl group-containing isocyanate compounds and organic monoisocyanates having good reactivity with isocyanate groups, and the resulting crosslinkable silyl group-containing poly (meth) acrylic monomers. Alcoholic hydroxyl group-containing (meth) acrylic monomers are preferable because of low viscosity of the resin, and specific examples thereof include hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, and hydroxyethyl. Hydroxyalkyl methacrylates such as methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, pentaerythritol triacrylate, glycerin monoacrylate, pentaerythritol diacreyl. Mono- or hydroxyl-remaining polyacrylates of polyhydric alcohols such as monostearate, dipentaerythritol pentaacrylate, ditrimethylolpropane triacrylate, polypropylene glycol monoacrylate, pentaerythritol trimethacrylate, glycerin monomethacrylate, pentaerythritol dimethacrylate monostearate. , Dipentaerythritol 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 And methoxides such as adducts of cyclohexene oxide and methacrylic acid Adducts of Le acid. 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,
Examples thereof include 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc methacrylate, and trimethylolpropane trimethacrylate. Among these, as the ethylenically unsaturated compound, from the viewpoint of weather resistance and properties after curing, a monomer of an acrylic acid ester compound, a monomer of a methacrylic acid ester compound, acrylamide, methacrylamide, acrylonitrile and the like (meth ) Acrylic compounds are preferred, and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2-
Ethylhexyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate are more preferable. Any of these may be used alone or in combination of two or more.

The crosslinkable silyl group-containing isocyanate compound may contain at least one isocyanate group and at least one crosslinkable silyl group in the molecule, but it is easy to control the reaction and the rubber after curing is cured. From the viewpoint of good elasticity, compounds having one isocyanate group and one crosslinkable silyl group in the molecule are preferable. The crosslinkable silyl group is preferably one represented by the following general formula, which is easy to produce and easy to crosslink.

[0030]

[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. a is an integer of 0, 1 or 2, and 0 or 1 is the most preferable. )

Specific examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and 3-isocyanatepropylmethyldimethoxysilane. Examples thereof include silane, 3-isocyanate propyl isopropoxy silane, isocyanate trimethoxy silane, and diisocyanate dimethoxy silane. These can be used alone or in combination of two or more. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.

The organic monoisocyanate is used for the purpose of adjusting the number of functional groups of the crosslinkable silyl group for adjusting the physical properties and for improving the water resistance, and may contain one isocyanate group in the molecule. , Does not contain a 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. Of these, aliphatic monoisocyanates are preferred. These may be used alone or in combination of two or more.

In the curable composition of the present invention, the proportion of the isocyanate group-containing urethane prepolymer / crosslinkable silyl group-containing poly (meth) acrylic resin is 10 parts by weight / 90 parts by weight to 99 parts by weight / 1 part by weight. Parts, more preferably 20 parts by weight / 80 parts by weight to 95 parts by weight / 5 parts by weight, particularly preferably 50 parts by weight / 50 parts by weight to 90 parts by weight / 10 parts by weight.

Next, the additives in the curable composition of the present invention will be described. As the additive in the present invention,
Examples include plasticizers, antioxidants, ultraviolet absorbers, crosslinking catalysts, fillers, coupling agents, thixotropic agents, storage stability improvers (dehydrating agents), and colorants.

The plasticizer is used for lowering the viscosity of the curable composition to improve workability, and the antioxidant and the ultraviolet absorber prevent oxidation, photodegradation and heat deterioration of the cured resin,
It is used to further improve heat resistance as well as weather resistance. Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants.

Specific examples of the plasticizer include phthalates such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate, dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate. Group carboxylic acid esters, alcohol esters such as pentaerythritol ester, phosphoric acid esters such as trioctyl phosphate and tricresyl phosphate,
Chlorinated paraffins, polyoxyalkylenes containing no hydroxyl groups obtained by etherification or esterification of the polyether polyols used in the synthesis of the above-mentioned isocyanate group-containing urethane prepolymers, especially saccharide polyhydric alcohols such as sucrose and ethylene oxide Polyoxyalkylene polyols obtained by etherification or esterification of polyoxyalkylene polyols obtained by addition polymerization of propylene oxide or propylene oxide, polyoxyalkylenes containing no hydroxyl group, and poly-α
Synthesis of polystyrene oligomers such as methylstyrene and polystyrene, poly (meth) acrylic resins, and above all, poly (meth) acrylic polyols used in the synthesis of the crosslinkable silyl group-containing poly (meth) acrylic resin. A poly (meth) acrylic resin having no hydroxyl group, which is obtained by polymerizing a compound having no hydroxyl group among the ethylenically unsaturated compounds also exemplified by the polymerization method described above, and has a number average molecular weight of 500 to 2,000. , Tg of −70 to −20 ° C., further −70 to −30 ° C., viscosity at 25 ° C. of 5,000 mPa · s or less poly (meth) acrylic resin, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, Isocyanates such as oligomers such as polyisoprene, polybutene, hydrogenated polybutene And a plasticizer which does not react with the groups, epoxidized soybean oil, epoxy-based plasticizers such as epoxy stearic acid benzyl, dibasic acid and polyester plasticizers such as polyesters from dihydric alcohols. The plasticizer is 0 to 300 parts by weight, especially 20 to 100 parts by weight based on 100 parts by weight of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing poly (meth) acrylic resin.
It is preferable to add 100 parts by weight.

As the hindered amine antioxidant,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, [decanedioic acid bis (2,2,2
6,6-Tetramethyl-1 (octyloxy) -4-piperidyl) ester, 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 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, dimethyl succinate 1- (2-hydroxyethyl)
-4-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-diyl} {(2,2,6,6-tetramethyl-
4-piperidyl) imino} hexamethylene {(2,2,
6,6-Tetramethyl-4-piperidyl) imino}],
N. N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,2
6,6-Pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate may be mentioned. Also, Asahi Denka Kogyo Co., Ltd., product name ADEKA STAB LA-
Also included are high molecular weight hindered amine antioxidants such as 63P and LA-68LD.

Examples of the hindered phenolic antioxidant include pentaerythritol-tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzene Examples include propanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester and 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

Examples of the ultraviolet absorber include 2-
A benzotriazole-based ultraviolet absorber such as (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (4,6-diphenyl-).
1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine ultraviolet absorbers, octabenzone and other benzophenone ultraviolet absorbers, 2,4-di-tert-butylphenyl -3,5-
Examples thereof include benzoate-based UV absorbers such as di-tert-butyl-4-hydroxybenzoate.

The antioxidant and the ultraviolet absorber are each 0.1 to 10 parts by weight based on 100 parts by weight of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing poly (meth) acrylic resin. It is particularly preferable to add 0.3 to 5 parts by weight.

The crosslinking catalyst is a catalyst for crosslinking (curing) an isocyanate group-containing urethane prepolymer or a crosslinkable silyl group-containing resin, and specifically, the known catalysts mentioned in the synthesis of the isocyanate group-containing urethane prepolymer are known. Examples of the urethane-forming catalysts, organometallic compounds, amines, etc., among which the organotin compounds having an excellent crosslinking rate are preferable. This organotin compound is specifically stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide,
Dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, and the like, among which dibutyltin dilaurate is the most preferable because it has a high crosslinking rate and is a liquid with relatively low toxicity and brilliance. . The crosslinking catalyst is 0.001 to 5 parts by weight, particularly 0.05 to 1 part by weight based on 100 parts by weight of the total of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing poly (meth) acrylic resin.
It is preferred to blend in parts by weight.

A filler, a coupling agent, a thixotropic agent, a storage stability improving agent (dehydrating agent), a coloring agent and the like are used in the curing of the present invention for the purpose of improving adhesion, reinforcing, preventing sagging and the like. It can be used by being blended with a sexual composition.

Examples of the filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, diatomaceous earth, fatty acid-treated calcium carbonate, and the like.
Those having a particle size of 0.01 to 100 μm are preferable, and among them, fatty acid-treated calcium carbonate is more preferable. Also, to reduce the specific gravity of the curable composition and the sealing material composition,
As a filler that imparts a texture to the cured surface and imparts a design property, various balloons (fine hollow bodies) of inorganic materials such as glass balloons, shirasu balloons, ceramic balloons, silica balloons, or phenol resins, urea resins,
Various balloons made of organic materials such as polystyrene and saran having a particle size of 50 to 400 μm can be mentioned.

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, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Examples thereof include low molecular weight compounds having an alkoxysilyl group such as γ-glycidoxypropylmethyldiethoxysilane and having a molecular weight of 500 or less, preferably 400 or less.

Examples of thixotropic agents include colloidal silica, asbestos powder, inorganic thixotropic agents such as the above-mentioned fatty acid-treated calcium carbonate, organic bentonites, modified polyester polyols, and organic thixotropic agents such as 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.

The total amount of the filler, the coupling agent, the thixotropic agent and the storage stability improver is 0 to 500 relative to 100 parts by weight of the total of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin. Parts by weight, especially 30 to 3
A range of 00 parts by weight is preferred.

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

In the curable composition of the present invention, if necessary, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, an aliphatic solvent such as n-hexane, and an alicyclic solvent such as cyclohexane. , Any one of conventionally known organic solvents such as an aromatic solvent such as toluene or xylene, which does not react with the crosslinkable silyl group and the isocyanate group, may be used alone or in combination of two or more kinds. You can 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 type from the viewpoint of workability. However, 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 of curing by curing.

[0052]

EXAMPLES The present invention will now be described in more detail by way of examples. Here, the sealing material composition is shown as an example of the curable composition, but the invention is not limited thereto. Synthesis Example 1 340 g of polyoxypropylene glycol (Exenol-3021 manufactured by Asahi Glass Co., Ltd., number average molecular weight 3,200) under a nitrogen gas flow in a heated reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube and a cooler. 100 g of polyoxypropylene triol (MN-4000 manufactured by Mitsui Chemicals Co., Ltd., number average molecular weight 4,000) and 90 g of toluene were charged, and 54 g of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) and dibutyltin dilaurate 0 Gradually add 0.05 g with stirring to 70
After stirring at -80 ° C for 2 hours, the reaction was terminated when the isocyanate group content became 1.09% by mass or less, to produce an isocyanate group-containing urethane prepolymer U-1. This isocyanate group-containing urethane prepolymer U
The measured isocyanate group content by titration of -1 is 1.0
0 mass% and the viscosity were 32,000 mPa * s / 25 degreeC.

Synthesis Example 2 A poly (meth) acrylic polyol (UH-200 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) was placed in a heating reaction vessel similar to that used in Synthesis Example 1.
0, number average molecular weight 4,900, weight average molecular weight 13,0
00, hydroxyl value 20.5 mg KOH / g, average number of hydroxyl groups 1.8), 800 g (OH equivalent: 0.29) were charged,
3-isocyanatopropyltrimethoxysilane (Y-5187 manufactured by Nippon Unicar Co., molecular weight 20 while stirring)
5.4) 30 g (NCO equivalent: 0.146) (R value (N
(CO equivalent / OH equivalent) = 0.5) and 0.08 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 70 to 80 ° C. for 2 hours, and the disappearance of the peak of the isocyanate group was confirmed by FTIR. It was cooled to room temperature. Next, in this, 43.1 g of octadecyl monoisocyanate (Millionate O manufactured by Hodogaya Chemical Co., Ltd., molecular weight 295) (N
After adding CO equivalent: 0.146) (R value (NCO equivalent / OH equivalent) = 1.0), the mixture was heated and stirred at 70 to 80 ° C. for 3 hours, and the peak of the isocyanate group disappeared by FTIR. Was confirmed, the reaction was terminated by cooling to room temperature. Obtained trimethoxysil-group-containing poly (meth)
Acrylic resin A-1 has a viscosity of 15,000 mPa · s
It was a transparent liquid at room temperature of / 25 ° C.

Synthesis Example 3 A poly (meth) acrylic polyol (UH-200 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) was placed in a heating reaction container similar to that used in Synthesis Example 1.
0, number average molecular weight 4,900, weight average molecular weight 13,0
00, hydroxyl value 20.5 mg KOH / g, average number of hydroxyl groups 1.8), 800 g (OH equivalent: 0.29) were charged,
3-isocyanatopropyltrimethoxysilane (Y-5187 manufactured by Nippon Unicar Co., molecular weight 20 while stirring)
5.4) 60.1 g (NCO equivalent: 0.29) (R value (NCO equivalent / OH equivalent) = 1.0) and 0.08 g of dibutyltin dilaurate were added, and then heated to 70-80.
The mixture was stirred at ℃ for 5 hours, the disappearance of the peak of the isocyanate group was confirmed by FTIR, and the mixture was cooled to room temperature. The obtained trimethoxysil group-containing poly (meth) acrylic resin A-2 was a transparent liquid at room temperature with a viscosity of 15,500 mPa · s / 25 ° C.

Example 1 600 g of the isocyanate group-containing urethane prepolymer U-1 obtained in Synthesis Example 1 was placed in a kneading container equipped with a heating and cooling device.
Then, 300 g of the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 obtained in Synthesis Example 2 was charged, and the mixture was stirred and mixed until the content became uniform to prepare a sealing material composition.

Example 2 The isocyanate group-containing urethane prepolymer U-1600 obtained in Synthesis Example 1 was placed in a kneading container equipped with a heating and cooling device.
g, trimethoxysilyl group-containing poly (meth) acrylic resin A-1 obtained in Synthesis Example 2 300 g, hindered phenolic antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals) and a hindered amine antioxidant: a compound represented by the following chemical formula (A) (Adeka Stab LA-63 manufactured by Asahi Denka Co., Ltd.)
P) (3 g) was charged, and the mixture was stirred and mixed until the content became uniform to prepare a sealant composition.

[0057]

[Chemical 2]

Example 3 The isocyanate group-containing urethane prepolymer U-1600 obtained in Synthesis Example 1 was placed in a kneading container equipped with a heating and cooling device.
g, 300 g of trimethoxysilyl group-containing poly (meth) acrylic resin A-2 obtained in Synthesis Example 3, hindered phenolic antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals, Inc.) and a hindered amine antioxidant: a compound represented by the chemical formula (A) (Adeka Stab LA-63 manufactured by Asahi Denka Co., Ltd.).
P) (3 g) was charged, and the mixture was stirred and mixed until the content became uniform to prepare a sealant composition.

Comparative Example 1 In the same manner as in Example 1 except that the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 was not used and 900 g of the isocyanate group-containing urethane prepolymer U-1 was used, Used as a sealing material.

Comparative Example 2 In the same manner as in Example 2, except that the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 was not used and 900 g of the isocyanate group-containing urethane prepolymer U-1 was used, A sealant composition was prepared.

[Performance Test] The following tests were performed using the sealing material compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2. (1) The weather-resistant sealant composition was formed into a sheet, and cured by curing at 23 ° C. and 50% relative humidity for 14 days to give a thickness of 0.2 mm and 5
mm sheet is manufactured, JIS K6266: 1996
For a 0.2 mm-thick sheet using a sunshine weatherometer in accordance with the above, the condition of the surface of the test piece after irradiation for 100 hours, irradiation for 500 hours, irradiation for 1000 hours, and irradiation for 2000 hours was measured for a sheet having a thickness of 5 mm. About 100 hours after irradiation, 500 hours after irradiation, 1000 times irradiation
The condition of the surface of the test piece was visually observed after a lapse of time, 2000 hours after irradiation, and 3000 hours after irradiation. The case where there were no or few hair cracks on the surface of the test piece was evaluated as ◯, and the case where there were many hair cracks on the surface of the test piece was evaluated as x. (2) Tensile Adhesion Property According to JIS A1439: 1997 “Testing method for building sealing material”, “4.21 Tensile Adhesion Test”, a tensile test was performed on a test body 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 sealant composition. In the tensile test, the modulus is 50% tensile stress M50 of 4.0 N / cm ² or more is ◯, M5
Those having 0 of less than 4.0 N / cm ² were evaluated as x. Elongation was evaluated as O when Emax was 300% or more, and as X when Emax was less than 300%. (3) Measurement of non-volatile content According to JIS K 6833 (1994) "General Test Method for Adhesives" 6.4 non-volatile content, sealant composition was applied to an aluminum foil dish molded to a diameter of 50 mm and a height of 30 mm. Weigh about 1.0g as a sample, weigh it,
It was dried in a hot air circulation type constant temperature bath at 105 ° C. for 3 hours, then allowed to cool and weighed. The non-volatile content was obtained by dividing the mass of the sample after drying by the mass of the sample before drying. The results and the composition of the sealant composition are summarized in Table 1.

[0062]

[Table 1]

Example 4 The isocyanate group-containing urethane prepolymer U-1500 obtained in Synthesis Example 1 was placed in a kneading container equipped with a heating and cooling device.
g, trimethoxysilyl group-containing poly (meth) acrylic resin A-1 obtained in Synthesis Example 2, hindered phenolic antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals), hindered amine antioxidant: a compound represented by the chemical formula (A) (Adeka Stab LA-63P manufactured by Asahi Denka Co., Ltd.)
3 g, penzotriazole-based UV absorber: 2- (3,
5-di-tert-butyl-2-hydroxyphenyl)
3 g of 5-chlorobenzotriazole (TINUVIN 327 manufactured by Ciba Specialty Chemicals), 350 g of calcium carbonate (N-2 manufactured by Maruo Calcium) treated with fatty acid (surface), 200 g of dioctyl phthalate and colloidal silica (Aerosil manufactured by Nippon Aerosil Co., Ltd.) 20
0) 50 g was charged, and the mixture was stirred and mixed until the content became uniform to prepare a sealant composition.

Example 5 A sealant composition was prepared in the same manner as in Example 4, except that 300 g of the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 was used.

Comparative Example 3 A sealing material composition was prepared in the same manner as in Example 4, except that the trimethoxysil group-containing poly (meth) acrylic resin A-1 was not used.

[Performance Test] Examples 4 and 5 and Comparative Example 3
The following tests were conducted using the sealing material composition prepared in. (1) The weather-resistant sealant composition was formed into a sheet, and cured by curing at 23 ° C. and 50% relative humidity for 14 days to give a thickness of 0.2 mm and 5
mm sheet is manufactured, JIS K6266: 1996
Using a sunshine weatherometer, a sheet with a thickness of 0.2 mm was measured for 100 hours after irradiation, 500 hours after irradiation, 1000 hours after irradiation, 2000 hours after irradiation, and 3000 hours after irradiation. , Thickness 5
mm sheet, after irradiation 100 hours, irradiation 500
The condition of the surface of the test piece was visually observed after a lapse of time, 1000 hours after irradiation, 2000 hours after irradiation, 3000 hours after irradiation, and 5000 hours after irradiation. The case where there were no or few hair cracks on the surface of the test piece was evaluated as ◯, and the case where there were many hair cracks on the surface of the test piece was evaluated as x. (2) Extrudability Measured in accordance with "4.14 Extrusion Test with Test Cartridge" of JIS A1439: 1997 "Testing Method for Building Sealing Materials" (measurement temperature 23 ° C). (3) 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). (4) Tensile Adhesion Property According to JIS A1439: 1997 “Testing Method for Building Sealing Materials”, “4.21 Tensile Adhesion Test”, after curing, after curing, it is immersed in water at 23 ° C. for 7 days and then cured. After 8
After heat treatment at 0 ° C. for 14 days, a tensile test was performed on each test body. The test body was prepared by treating the slate with a primer (OP2531, manufactured by Auto Kagaku Kogyo Co., Ltd.), casting and curing the sealant composition. The modulus has a 50% tensile stress (M50) value of 4.0 N / cm ^2.
The above items were evaluated as ◯, and those less than 4.0 N / cm ² were evaluated as x. Elongation has an Emax of 300 in a tensile test.
% Or more was evaluated as ◯, and less than 300% was evaluated as x. Table 2 collectively shows these results and the composition of the sealing material composition.

[0067]

[Table 2]

[0068]

As described above, the curable resin component in the present invention has a low viscosity, and has a low modulus, a large elongation and a high strength after curing. Therefore, a curable composition containing the curable resin component has excellent workability. In addition, the adhesiveness after curing is excellent. Further, the curable composition of the present invention, in addition to the above-mentioned properties, has particularly excellent weather resistance and excellent durability such as heat resistance and water resistance, so that recent constructions, civil engineering,
It can be adequately adapted to ultra long life and high performance of automobiles. Therefore, the curable composition of the present invention is for construction,
It is suitable for adhesives for civil engineering and automobiles, waterproofing materials, and sealing materials, especially sealing materials with extremely long life and high performance, such as joints for outer walls of buildings, joints for civil engineering, and joints for automobiles.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 3/10 C09K 3/10 E G F term (reference) 4H017 AA04 AB02 AB04 AB16 AC05 AC16 AE03 AE05 4J002 AC063 AC093 AE053 BB183 BC023 BG043 BG07X BL013 CD003 CD163 CF003 CH023 CK02W CK04W DE239 DJ009 DJ019 DJ039 DJ049 DL009 EE038 EH036 EH046 EH096 EH146 EJ017 EJ027 EJ037 EN037 EU137 EU178 EU187 EU188 EW046 FA109 FB089 FD019 FD023 FD026 FD058 FD077 FD090 FD140 FD200 GL00 GN00 4J034 DF01 DF02 DG01 DP12 DP18 HA01 HC01 HC03 HC12 HC13 HC18 HC61 HC64 HC67

Claims (7)

[Claims] 1. A curable composition comprising an isocyanate group-containing urethane prepolymer and a crosslinkable silyl group-containing polyacrylic and / or methacrylic resin as curing components. 2. The isocyanate group-containing urethane prepolymer obtained by reacting an organic polyisocyanate and a high molecular weight polyether polyol under the condition of excess isocyanate groups with respect to hydroxyl groups. The curable composition according to claim 1, which is a polymer. 3. The crosslinkable silyl group-containing polyacrylic and / or methacrylic resin is a resin obtained by reacting a polyacrylic and / or methacrylic polyol with a crosslinkable silyl group-containing isocyanate compound. Item 3. The curable composition according to Item 1 or 2. 4. The crosslinkable silyl group-containing polyacrylic and / or methacrylic resin is obtained by reacting a polyacrylic and / or methacrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and an organic monoisocyanate. The curable composition according to claim 1 or 2, which is a resin. 5. The curable composition according to claim 1, further comprising an additive. 6. The method according to claim 5, wherein the additive is a plasticizer, an antioxidant, an ultraviolet absorber, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent and / or a storage stability improver. Curable composition. 7. A sealant composition comprising an isocyanate group-containing urethane prepolymer and a crosslinkable silyl group-containing polyacrylic and / or methacrylic resin as curing components.