JP2000327771A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hardenable composition capable of both imparting high tensile strength to a hardened product and rapidly being hardened by including a reactive silicon group-containing polyether oligomer having at least one reactive silicon group. SOLUTION: This composition contains a reactive silicon group-containing polyether oligomer having at least one reactive silicon group expressed by the formula, O-R1-CH(CH3)-CH2-SiX3 [wherein R1 is a 1-20C bivalent organic group containing at least one selected from the group consisting of H, O and N; and X is OH or a hydrolyzable group (e.g. an alkoxyl such as methoxyl, ethoxyl, propoxyl, isopropoxyl or the like)], concretely e.g. O-CH2-CH(CH3)-CH2- Si(OCH3)3. The reactive silicon group-containing polyether oligomer is obtained e.g. by introducing at least one unsaturated bond into a polyether oligomer having at least one hydroxyl group, followed by reacting a compound having at least one reactive silicon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition containing a novel reactive silicon group-containing polyether oligomer.

[0002]

2. Description of the Related Art Hitherto, room temperature curable compositions containing a reactive silicon group-containing polyether oligomer and a specific silanol condensation catalyst have been known and have been used for sealants, adhesives and the like. Conventional reactive silicon group-containing polyether oligomers have a limit in the rate of introduction of silyl groups to the polymer terminals, and therefore have a limit in tensile strength. Therefore, when searching for a method for improving the introduction rate of a silyl group, it was found that a polymer having an allyl group at the terminal used in the hydrosilylation reaction, which is a method for introducing a silyl group, was changed to a polymer having a methallyl group at the terminal. I found that it was effective. However, it was revealed that the curable composition using the obtained high tensile strength polymer had a reduced initial curing rate due to a methyl group caused by a methallyl group. Therefore, it is difficult to use it for industrial adhesives and the like that require fast curing, and it is necessary to improve the curing speed.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a reactive silicon group-containing polyether oligomer having a higher tensile strength than a conventional curable composition, but having a slower curing, while preventing a decrease in physical properties while preventing a decrease in physical properties. It is an object of the present invention to provide a curable composition having both high tensile strength and fast curing, which has improved stiffness.

[0004]

The first aspect of the present invention is as follows.
General formula (1): —O—R ¹ —CH (CH ₃ ) —CH ₂ —SiX ₃ (1) (wherein R ¹ constitutes one or more selected from the group consisting of hydrogen, oxygen, and nitrogen) X represents a divalent organic group having 1 to 20 carbon atoms contained as an atom, and X represents a hydroxyl group or a hydrolyzable group). It relates to a curable composition.

In a preferred embodiment, the present invention relates to the curable composition, wherein R ¹ is CH ₂ .

In a further preferred embodiment, X is OC
The curable composition is H ₃ .

[0007] As another preferred embodiment, the polyether oligomer _{-O-CH 2 -CH (CH 3} ) = CH 2 introduced an unsaturated bond represented by the following formula, a compound having a reactive silicon group H -Si (OCH ₃ ) ₃ and a reactive silicon group-containing polyether oligomer having a reactive silicon group shown below, which is obtained by reacting in a system containing a catalyst and a sulfur compound in an atmosphere containing oxygen. The present invention relates to the above curable composition. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (OCH ₃ ) _{3 In} another more preferred embodiment, 85% or more of the terminals of the reactive silicon group-containing polyether oligomer are reactive silicon. The present invention relates to the curable composition, which is a base.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The reactive silicon group-containing polyether oligomer used in the present invention has the general formula (1): -OR ¹ -CH (CH ₃ ) -CH _2- Si (X) ₃ (1) (wherein R ¹ is a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen, and nitrogen as a constituent atom) And X represents a hydroxyl group or a hydrolyzable group) as long as it is a polyether-based oligomer containing at least one structure represented by the following formula in the side chain or terminal, and having a main chain of polyether.

R ¹ is a divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of hydrogen, oxygen and nitrogen as a constituent atom.
_{2 -, - C 2 H 4} -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10
_{-, - C 6 H 4 -} , - C 6 H 12 -, - C 7 H 14, -C 8 H 16
_{-, - C 9 H 18 -} , - C 10 H 20 -, - CH (CH 3) -,
_{-CH 2 -CH (CH 3) -} , - CH 2 -CH (CH 3) -
CH ₂ —, —C ₂ H ₄ —CH (CH ₃ ) —, —CH ₂ —C ₆ H
_{4 -, - CH 2 -C 6} H 4 -CH 2 -, - C 2 H 4 -C 6 H
_{4 -, - C (O)} -, - C (O) -CH 2 -, - C (O)
_{-C 6 H 4 -, - C} (O) -NH -, - C (O) -NH-
CH ₂ —, —C (O) —NH—C ₆ H ₄ —, —C (O)
-O -, - C (O) -O-CH 2 -, - C (O) -O-
Examples are groups such as C ₆ H ₄ —. -CH ₂ in terms of easy synthesis _{-, - C 2 H 4 -} , - CH 2 -CH (CH 3) -,
—C (O) — and —C (O) —NH— are preferred, and —CH ₂ — is particularly preferred because of availability of raw materials.

The reactive silicon group contained in the reactive silicon group-containing polyether oligomer represented by the general formula (1) includes a group represented by the general formula (2): —SiX ₃ (2). (Wherein X represents a hydroxyl group or a hydrolyzable group) The hydrolyzable group in the above X is not particularly limited, and may be any conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group,
Ketoximate group, amino group, amide group, acid amide group,
Examples include an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group is preferable in terms of gentle hydrolysis and easy handling.

Specifically, a reactive silicon group-containing polyether oligomer having a reactive silicon group represented by the following formula is preferred. —O—CH ₂ —CH (CH ₃ ) —CH ₂ —Si (OCH ₃ ) ₃ The molecular weight of the polyether oligomer of the present invention is not particularly limited, but the number average molecular weight in terms of polystyrene by GPC is 1,000. To 100,000. When the number average molecular weight is less than 1,000, the obtained cured product of the reactive silicon group-containing polyether oligomer becomes brittle, and when it exceeds 100,000, the functional group concentration becomes too low, and the curing rate decreases. It is not preferable because the viscosity becomes too high and handling becomes difficult. Further, the number average molecular weight is from 1,000 to 50,000.
It is particularly preferable that it is 0 from the viewpoint of the viscosity of the obtained reactive silicon group-containing polyether oligomer.

The main chain structure of the polyether oligomer may be any polymer having a structure represented by —RO— as a repeating unit, wherein R is hydrogen, oxygen,
And a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of nitrogen and nitrogen as a constituent atom. Further, a homopolymer in which all of the repeating units are the same, or a copolymer containing two or more types of repeating units may be used. Further, the main chain may have a branched structure. In the present invention, for example, a hydroxy group-containing polyether obtainable by the following various methods can be used.

In order to obtain the present invention, alkylene oxides, specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide, and Alkyl or allyl or aryl glycidyl ethers, specifically methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc. Using unsubstituted epoxy, ethylene glycol, propylene glycol,
Butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylol Polyethers obtained by ring-opening polymerization in the presence of various catalysts using dihydric alcohols or polyhydric alcohols such as methane, trimethylolpropane, pentaerythritol and various oligomers having a hydroxyl group as initiators can be used. . Known polymerization catalysts include KOH, NaOH and other alkaline catalysts, trifluoroborane-etherate and other acidic catalysts, and aluminoporphyrin metal complexes and cobalt zinc zinc cyanide-glyme complex catalysts and other known metal cyanide complex catalysts. Things are used. In particular, it is preferable to use a double metal cyanide complex catalyst having few side reactions, but other catalysts may be used.

As a method for producing the reactive silicon group-containing polyether oligomer from the hydroxyl group-containing polyether oligomer, a known method may be used. For example, an unsaturated bond may be added to the hydroxyl group-containing polyether oligomer. After the introduction, a method of reacting a compound having a reactive silicon group may be mentioned.

Examples of a method for introducing an unsaturated bond into a polyether oligomer having a hydroxyl group include a method for forming a bond by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like. For example, when an unsaturated group is introduced by an ether bond, -OM (M is N
a or K), after the formation of the general formula (3): H ₂ C ＝ C (CH ₃ ) —R ¹ —Y (3) (where R ¹ is selected from the group consisting of hydrogen, oxygen and nitrogen) And a method of producing a polyether having an unsaturated group by reacting with a divalent organic group having 1 to 20 carbon atoms containing at least one kind as a constituent atom and Y being a halogen). .

As a method for reacting a compound having a reactive silicon group with a polyether oligomer into which an unsaturated bond has been introduced, a hydrosilylation reaction carried out in the presence of a catalyst may be mentioned. In the hydrosilylation reaction, in order to accelerate the reaction, it is preferable to perform the reaction in an atmosphere containing oxygen and to add an additive such as a sulfur compound.

The compound having a reactive silicon group used in the hydrosilylation reaction includes one or more silicon groups bonded to the above-mentioned hydroxyl group or hydrolyzable group in the molecule, and one or more silicon-hydrogen groups. Any compound having a group in the molecule may be used. Typical examples include a compound represented by the following general formula (4). General formula (4): H—SiX ₃ (4) (X is the same as the group described in the above general formula (1)) Specifically, trichlorosilane; trimethoxysilane, triethoxysilane Alkoxysilanes such as;
Examples include acyloxysilanes such as triacetoxysilane; ketoximesilanes such as tris (acetoxymate) silane; and alkenyloxysilanes such as tris (isopropenoxy) silane. Of these,
Particularly, alkoxysilanes are preferable, and a methoxy group is particularly preferable among the alkoxy groups.

As a specific example of the above hydrosilylation reaction, an unsaturated compound represented by the general formula (5): —O—R ¹ —CH (CH ₃ ) ＝ CH ₂ (5) (R ¹ is the same as above) A polyether oligomer having a bond introduced therein, and a reactive silicon group represented by the general formula (6): H-SiX ₃ (6) (X is the same as the group described in the general formula (1)) A reactive silicon group-containing polyether oligomer having a reactive silicon group obtained by reacting a compound having an oxygen-containing atmosphere with a catalyst and a system in which a sulfur compound is present is preferable, and further represented by the following formula: that polyethers was introduced an unsaturated bond oligomer _{-O-CH 2 -CH (CH 3} ) = compound having CH ₂ with a reactive silicon group H-Si and (OCH _{3) 3} in an atmosphere having an oxygen, a catalyst And sulfur compounds are present More preferred reactive silicon group-containing polyether oligomer -O-CH ₂ -CH having reactive silicon groups shown below obtained by reacting _{(CH 3) -CH 2 -Si (} OCH 3) 3 in the middle.

Further, in the present invention, the hydrolyzable group X in the obtained silyl group can be converted to another hydrolyzable group. In particular, when the X group is a halogen, the compound is preferably converted to another hydrolyzable group since hydrogen halide having a strong pungent odor is generated upon curing with moisture. As the hydrolyzable functional group that can be converted, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
Examples include an aminooxy group and a mercapto group.
There are various methods for converting a halogen functional group into these hydrolyzable functional groups. For example, as a method for converting to an alkoxy group, methanol, ethanol, 2-methoxyethanol, sec-butanol, t
alcohols and phenols such as er-butanol and phenol; alkoxides of alcohols and phenols such as sodium, potassium and lithium; orthoformates such as methyl orthoformate and ethyl orthoformate; ethylene oxide; propylene oxide; A specific example is a method of reacting an epoxy compound such as allyl glycidyl ether with a halogen functional group. Particularly, the reaction can be easily carried out by using a reaction system consisting of alcohols and phenols and epoxy compounds in combination with alcohols and phenols and orthoformate esters combined with and. And obtains favorable results. Similarly, as a method for converting into an acyloxy group, a method of reacting a carboxylic acid such as acetic acid and propionic acid, an acid anhydride such as acetic anhydride, a sodium salt, a potassium salt and a lithium salt of a carboxylic acid; Is specifically exemplified. Similarly, methods for converting to an aminooxy group include hydroxylamines such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-methylphenylhydroxylamine and N-hydroxylpyrrolidine; Sodium salts,
Specific examples include a method of reacting a potassium salt and a lithium salt with a halogen functional group. Similarly, as a method of converting to an amide group, N, N-dimethylamine,
A method of reacting primary and secondary amines such as N, N-diethylamine, N-methylphenylamine and pyrrolidine, sodium salts, potassium salts and lithium salts of primary and secondary amines with a halogen functional group. Specific examples are given below. Similarly, as a method of converting to an acid amide,
Specific examples include a method of reacting an acid amide having at least one hydrogen atom on a nitrogen atom such as acetamide, formamide and propionamide, a sodium salt, a potassium salt and a lithium salt of the acid amide with a halogen functional group. It is listed. Ketoximes such as acetoxime and methyl ethyl ketoxime; and the use of a reaction system in which a mercaptan such as N-octyl mercaptan and t-butyl mercaptan is combined with an orthoformate or an epoxy compound, the ketoximate group and the mercapto group, respectively. Some can be converted and the other can be converted to alkoxyl groups derived from orthoformate or epoxy compounds. As described above, it is also possible to convert various hydrolyzable functional groups to other hydrolyzable functional groups and use them instead of converting to other hydrolyzable functional groups only in the case of halogen functional groups.

The hydrosilylation reaction in the production method of the present invention is usually at 10 to 150 ° C., preferably at 20 to 120 ° C.
° C, more preferably in the range of 40 to 100 ° C. If necessary, such as adjustment of the reaction temperature and adjustment of the viscosity of the reaction system, benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, Hexane,
Solvents such as heptane can be used.

The catalyst used in the reaction between the polyether oligomer having an unsaturated bond introduced therein and the compound having a reactive silicon group is selected from Group VIII transition metal elements such as platinum, rhodium, cobalt, palladium and nickel. A metal complex catalyst or the like is effectively used. For example,
_{H 2 PtCl 6 · 6H 2 O} , platinum - vinylsiloxane complex, a platinum - olefin complexes, Pt metal, RhCl (P
Ph ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , I
_{rCl 3, FeCl 3, AlCl 3} , PdCl 2 · 2H
Compounds such as ₂ O, NiCl ₂ , TiCl _{4 and} the like can be used, but from the viewpoint of hydrosilylation reactivity, it is particularly preferable to be either a platinum-vinylsiloxane complex or a platinum-olefin complex. The term "platinum-vinylsiloxane complex" as used herein is a generic term for a compound in which a siloxane, a polysiloxane, or a cyclic siloxane is coordinated with a platinum atom having a vinyl group in the molecule as a ligand. Specific examples of the child include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the like. Specific examples of the olefin ligand of the platinum-olefin complex include 1,5-hexadiene, 1,7-octadiene, 1,9
-Decadiene, 1,11-dodecadiene, 1,5-cyclooctadiene and the like. Among the above ligands, 1,9-decadiene is particularly preferred.

The platinum-vinylsiloxane complex, platinum-
The olefin complex is disclosed in JP-B-8-9006.

The amount of the catalyst used is not particularly limited, but it is usually preferable to use 10 ^-1 to 10 ^-8 mol of a platinum catalyst per mol of alkenyl group, more preferably ¹ to 10 ^-8 mol.
It can be used in the range of 0 ^-3 to 10 ^-6 mol. If the amount of the catalyst is small, the hydrosilylation reaction may not proceed sufficiently. Further, if the amount of the catalyst is too large, there is a problem that the cost burden due to the consumption of the catalyst increases and the amount of the catalyst remaining in the product increases.

In terms of accelerating the hydrosilylation reaction, reactivation of the catalyst by use of oxygen is disclosed in Japanese Patent Application Laid-open No. Hei 8-28.
It is preferable to add 3339) or a sulfur compound. The addition of the sulfur compound contributes to a reduction in the production time, a reduction in the production cost, and an increase in the productivity without causing a problem such as an increase in the cost of the expensive platinum catalyst or a problem of removing the residual catalyst. Examples of the sulfur compound include simple sulfur, thiol, sulfide, sulfoxide, sulfone, thioketone, and the like. Sulfur is particularly preferred, but is not limited thereto. In order to add the sulfur compound to the liquid phase reaction system, for example, the sulfur compound can be dissolved and mixed in advance in a part of the reaction solution or the solvent and then uniformly dispersed throughout. For example, the compound can be added after dissolving a sulfur compound in an organic solvent such as toluene, hexane, or xylene.

The amount of the sulfur compound to be added is, for example, 0.1 to 10 times the amount based on the number of moles of the metal catalyst,
Or 0.002 based on the number of moles of the alkenyl group.
0.1 times the amount, or 1 based on the total weight of the reaction solution.
It can be set within a range of about 500 ppm. If the amount is small, the effect of the present invention may not be sufficiently achieved. If the amount of the sulfur compound is too large, a problem such as a decrease in the catalytic activity or an inhibition of the reaction may occur. Therefore, it is preferable to appropriately select the addition amount.

The hydrosilylation reaction in the production method of the present invention can be carried out without a solvent or in the presence of a solvent. As the solvent for the hydrosilylation reaction, usually, hydrocarbons, halogenated hydrocarbons, ethers and esters can be used, but heptane, hexane, benzene,
It is preferable to use toluene and xylene. In particular, when performing hydrosilylation of a polymer compound, a method using a solvent is preferable for liquefaction or viscosity reduction. The plasticizer added in the step of commercializing the polymer compound may be used as the reaction solvent. Examples of such a plasticizer include polybutene, hydrogenated polybutene, α-methylstyrene oligomer, biphenyl, triphenyl,
Hydrocarbon compounds such as triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, and alkyldiphenyl, BAA-15 (Daichi Kagaku), P-103, W320 (Dainippon Ink), PN-
Adipate compounds such as 150 (Adeka Argus), TOTM, TITM (New Nippon Rika), W-700
(Dainippon Ink) and other trimellitic acid ester compounds, NS-100, NM-26, NP-24, PS-3
2, petroleum-based process oils such as PW-32, PX-32 (Idemitsu Kosan), alkene-68 (Nippon Petroleum Detergent), B
F-1000 (Adeka Argus), KE-828 (Arakawa Chemical), DOTP (Shin Nippon Rika), and the like are preferable, and alkene-68, PS-3 is preferred in that heating loss is small.
2, PW-32, PX-32, DOTP, NS-10
0, TOTM, etc. are particularly preferred, but are not necessarily limited thereto.

In the hydrosilylation reaction in the production method of the present invention, the gas phase of the reactor used for the hydrosilylation reaction may consist solely of an inert gas such as nitrogen or helium, or may contain oxygen or the like. Is also good. When performing a hydrosilylation reaction, the reactor gas phase may be carried out in the presence of an inert gas such as nitrogen or helium from the viewpoint of safety in handling combustible substances. However, when the reactor gas phase is carried out in the presence of an inert gas such as nitrogen or helium, the reaction rate may decrease depending on the reaction system conditions for hydrosilylation.

In the hydrosilylation reaction in the production method of the present invention, the oxygen concentration in the gas phase of the reactor is set to a value that avoids the explosive mixed composition, thereby promoting the hydrosilylation reaction safely in the presence of oxygen. Can be. The oxygen concentration in the gas phase of the reactor can be, for example, 0.5 to 10%. Furthermore, in order to suppress oxidation of the polyether oligomer, the reaction solvent, the plasticizer in the system, and the like in the hydrosilylation reaction by oxygen, the hydrosilylation reaction can be performed in the presence of an antioxidant. As the antioxidant, a phenolic antioxidant having a function of a radical chain inhibitor, for example, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl -6-tert-butylphenol, 2,2'-methylenebis (4-methyl-6-t
tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol),
4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakisdimethylene-3 (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate @ methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like can be used. As similar radical chain inhibitors, amine antioxidants such as phenyl-β-
Naphthylamine, α-naphthylamine, N, N′-di-
Although sec-butyl-p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine and the like can be used, the present invention is not limited thereto.

According to the production method of the present invention, a reactive silicon group-containing polyether oligomer characterized in that the number of reactive silicon-containing groups is at least 85% of the number of terminals of the polyether oligomer on average. It is possible. Various methods can be considered for measuring the silylation rate. At present, an accurate value can be obtained by a measurement method using NMR. By calculating the ratio of the terminal into which the reactive silicon-containing group has been introduced to the terminal not having been introduced by NMR, the silyl group introduction ratio can be determined.

The reactive silicon group-containing polyether oligomer of the present invention, when mixed with a silanol condensation catalyst, is cured at room temperature with atmospheric moisture to give a coating film having good adhesion to metal, glass, etc. It is useful as a coating composition, a sealing composition, a coating composition, and an adhesive composition for articles, aircraft, automobiles and the like.

Examples of the silanol condensation catalyst include titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; dibutyltin oxide; Reaction products with phthalic acid esters; dibutyltin diacetylacetonate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelate compounds such as; lead octylate; butylamine, octylamine, dibutylamine, monoethanol Amine, diethanolamine, thoria ethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,
Xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole,
1,8-diazabicyclo (5,4,0) undecene-7
Amine compounds such as (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; γ-
Silanol condensation catalysts such as silane coupling agents having an amino group such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other known acidic catalysts and basic catalysts such as acidic catalysts and basic catalysts. And a silanol condensation catalyst. These catalysts may be used alone or in combination of two or more. Of these, tin (II) salts of organic carboxylic acids such as tin octylate, tin laurate, and tin ferzatic acid are particularly preferred.

The amount of these silanol condensation catalysts used is
0.01 to 100 parts by weight of the oxyalkylene polymer
About 20 parts by weight, more preferably about 0.1 to 10 parts by weight. If the amount of the silanol condensation catalyst used is too small relative to the oxyalkylene polymer, the curing rate becomes slow, and the curing reaction does not easily proceed sufficiently.
Not preferred. On the other hand, if the amount of the silanol condensation catalyst used is too large relative to the oxyalkylene polymer, local heat generation or foaming occurs during curing, and it is difficult to obtain a good cured product, which is not preferable.

The curable composition of the present invention may contain various plasticizers, fillers, solvents, adhesion-imparting agents such as aminosilane, dehydrating agents, and other additives, if necessary.

Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, dioctyl adipate, and dioctyl. Non-aromatic dibasic acid esters such as sebacate, and phosphate esters such as tricresyl phosphate and tributyl phosphate, and the like. As a relatively high molecular weight type plasticizer, for example, dibasic acid and dihydric alcohol And polyethers such as polypropylene glycol and derivatives thereof, and polystyrenes such as poly-α-methylstyrene and polystyrene.

In particular, the use of polyethers is preferred in order to prevent the storage stability of the composition and the curing rate after storage from lowering.

These plasticizers can be used alone or as a mixture. These plasticizers are used in an amount of about 20 to 400 parts by weight based on 100 parts by weight of the reactive silicon group-containing polyether oligomer.

Specific examples of the filler include wood powder, walnut shell powder, rice husk powder, pulp, cotton chip, mica, graphite, diatomaceous earth, terra alba, kaolin, clay, talc, silicic anhydride, Inorganic fillers such as quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass beads, magnesium carbonate, titanium oxide, alumina, glass balloon, shirasu balloon, silica balloon, calcium oxide, magnesium oxide, and silicon oxide Examples of the organic filler include powdered rubber, recycled rubber, fine powder of thermoplastic or thermosetting resin, and hollow bodies such as polyethylene. These fillers may be used alone or in combination of two or more. The amount of the filler used is preferably about 3 to 300 parts with respect to 100 parts by weight of the polyether oligomer of the component (A) from the viewpoint of workability,
About 10 to 150 parts is more preferable. Specific examples of the solvent include hydrocarbons such as toluene, xylene, n-hexane and cyclohexane, acetates such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, isopropanol and n-butanol, and ethyl cellosolve. , Butyl cellosolve, ethers such as cellosolve acetate, methyl ethyl ketone, ethyl acetoacetate,
Non-reactive solvents such as ketones such as acetylacetone, diacetone alcohol, methyl isobutyl ketone, acetone, cyclohexanone, cyclooctanone, and the like, are not particularly limited as long as they are such solvents.

Specific examples of the adhesiveness-imparting agent include:
Amino-containing alkoxysilanes or amino-substituted alkoxysilane derivative compounds are preferred.

Specific examples of the amino-containing alkoxysilane or amino-substituted alkoxysilane derivative include:
H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ N
H (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH
(CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ O) ₂
Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (O
Amino-substituted alkoxysilane such as CH ₃ ) _3, and the above-mentioned amino-substituted alkoxysilane and CH ₂ (O) CHCH ₂
O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , —CH ₂ CH ₂ Si (O
A reaction product with an epoxysilane compound such as CH ₃ ) ₃ or
CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OC
_{H 3) 3, CH 2 =} C (CH 3) COO (CH 2) 3 Si (O
A reaction product with a methacryloxysilane compound such as CH ₂ CH ₂ OCH ₃ ) ₃ is exemplified. The reaction between an amino-substituted alkoxysilane and an epoxysilane compound or an acryloylsilane compound is performed by the amino-substituted alkoxysilane 1
The compound can be easily obtained by mixing 0.2 to 5 mol of the silane compound with respect to the mol and stirring the mixture at room temperature to 180 ° C. for 1 to 8 hours.

The above amino-substituted alkoxysilane or
The amino group-substituted alkoxysilane derivative compound is preferably used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polyether polymer having a crosslinkable hydrolyzable silyl functional group at the terminal. If the amount is less than 0.01 part by weight, the expected adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured rubber are adversely affected.

As a specific example of the dehydrating agent, a dehydrating agent having a hydrolyzable group bonded to a silicon atom which reacts more easily with H ₂ O than a silicon group in the reactive silicon group-containing polyether oligomer is preferable. Usually, those having a molecular weight of 300 or less are preferred.

Examples of the hydrolyzable functional group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an aminooxy group, an amide group and an alkenyloxy group. Examples of the substituent include an epoxy-containing group, an amino-containing group, an acryl-containing group, and a mercapto-containing group. Specific examples of such compounds include: Si
(OC ₂ H ₅ ) ₄ , CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ , CH ₂
ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OA
c) ₃ , CH ₃ —Si [ON = C (CH ₃ ) (C
₂ H ₅ )] ₃ , CH ₃ Si [N (CH ₃ ) ₂ ] ₃ , CH ₃ Si
[N (CH ₃ ) (C ₂ H ₅ )] ₃ , CH ₃ Si [N (CH ₃ )
Ac] ₃ , CH ₃ Si [0C (C ₂ H ₅ ) = CH ₂ ] ₃ , CH
₂ (O) CHCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C
H ₂ (O) CHCH ₂ O (CH ₂ ) ₃ Si (OCH ₂ CH ₃ )
₃ , CH ₂ CH ₂ Si (0CH ₃ ) ₃ , CH ₂ CH ₂ Si (O
CH ₂ CH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃
Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (C
_{H 2) 3 Si (OCH 2} CH 3) 3, HS (CH 2) 3 Si
(OCH ₃ ) ₃ , HS (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃
And the like. These dehydrating agents can be used alone or in combination. These dehydrating agents are used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the reactive silicon group-containing polyether oligomer.
It is preferable to use about 0 parts by weight. Examples of the other additives include anti-sagging agents such as hydrogenated castor oil, organic bentonite and calcium stearate, and anti-aging agents such as coloring agents, ultraviolet absorbers and light stabilizers.

The method for producing the curable composition containing the reactive silicon group-containing polyether oligomer of the present invention is not particularly limited. For example, the reactive silicon group-containing polyether oligomer, the curing catalyst, and other additives are blended. And kneading using a mixer, roll or kneader, etc.,
An ordinary method such as dissolving and mixing each component using a solvent can be adopted. The composition may be a one-pack or two-pack composition.

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EXAMPLES In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited to these examples. Synthesis Example 1 Bifunctional polypropylene oxide 500 having a molecular weight of 10,000 and both ends being a methallyl group in a 1 L autoclave
g, 10 g of hexane and azeotropic dehydration at 90 ° C.
After the hexane was distilled off under reduced pressure, the inside of the vessel was replaced with 8% O ₂ / N ₂ . 25 μl of sulfur (1% by weight toluene solution) and 56 μl of a platinum divinyldisiloxane complex (3% by weight xylene solution in terms of platinum) were added thereto, and 27.9 g of trimethoxysilane was added dropwise. After the mixed solution was reacted at 90 ° C. for 5 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyether oligomer (a). The number average molecular weight of the obtained reactive silicon group-containing polyether oligomer (a) is about 1
It was 0000. Synthesis Example 2 Bifunctional polypropylene oxide 500 having a molecular weight of 10,000 and a methallyl group at both ends in a 1 L autoclave
g, 10 g of hexane and azeotropic dehydration at 90 ° C.
After the hexane was distilled off under reduced pressure, the inside of the vessel was replaced with 8% O ₂ / N ₂ . To this, 25 μl of sulfur (1% by weight in toluene solution) and 56 μl of a platinum divinyldisiloxane complex (3% by weight of xylene solution in terms of platinum) were added, and 24.2 g of dimethoxymethylsilane was added dropwise. After the mixed solution was reacted at 90 ° C. for 5 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyether oligomer (b). The number average molecular weight of the obtained reactive silicon group-containing polyether oligomer (b) was about 10,000. Synthesis Example 3 1-L Autoclave, Molecular Weight 1 at Which Both Terminals Are Allyl Groups
500 g of 000 polypropylene oxide and 10 g of hexane were added, azeotropic dehydration was performed at 90 ° C., hexane was distilled off under reduced pressure, and the atmosphere was replaced with nitrogen. On the other hand, 30 μl of platinum divinyldisiloxane complex (3% by weight in terms of platinum)
Was added dropwise, and 9.0 g of dimethoxymethylsilane was added dropwise. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyether oligomer (c). The number average molecular weight of the obtained reactive silicon group-containing polyether oligomer (c) was about 10,000. Example 1 A curable composition having the composition shown in Table 1 was prepared using the reactive silicon group-containing polyether oligomer (a). A sheet having a thickness of 3 mm was formed from the obtained curable composition, and after curing, a JIS No. 3 dumbbell was punched out. Obtained JIS
The tensile strength (100% tensile stress) of No. 3 dumbbell was measured, and the results are shown in Table 2. Example 2 A curable composition having the composition shown in Table 1 was prepared using the reactive silicon group-containing polyether oligomer (a). A sheet having a thickness of 3 mm was prepared from the obtained curable composition, and the time until the compound did not adhere even when the surface was touched with a spatula (skinning time) was measured. The results are shown in Table 2. Comparative Example 1 Reactive silicon group-containing polyether oligomer (b),
Using (c), a curable composition having the composition shown in Table 1 was prepared. A sheet having a thickness of 3 mm was formed from the obtained curable composition, and after curing, a JIS No. 3 dumbbell was punched out. The tensile strength (100% tensile stress) of the obtained JIS No. 3 dumbbell was measured, and the results are shown in Table 2. Comparative Example 2 Reactive silicon group-containing polyether oligomer (b),
Using (c), a curable composition having the composition shown in Table 1 was prepared. A sheet having a thickness of 3 mm was prepared from the obtained curable composition, and the time until the compound did not adhere even when the surface was touched with a spatula (skinning time) was measured.
Shown in

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

According to the present invention, it is possible to obtain a curable composition having both high tensile strength and rapid curing, which was impossible with a curable composition having a reactive silicon group-containing polyether oligomer hitherto.

Claims (5)

[Claims] 1. General formula (1): —O—R ¹ —CH (CH ₃ ) —CH ₂ —SiX ₃ (1) (wherein R ¹ is selected from the group consisting of hydrogen, oxygen and nitrogen) X represents a divalent organic group having 1 to 20 carbon atoms containing at least one kind as a constituent atom, and X represents a hydroxyl group or a hydrolyzable group. A curable composition containing an ether oligomer. 2. The curable composition according to claim 1, wherein R ¹ is CH ₂ . 3. The curable composition according to claim 1, wherein X is OCH ₃ . 4. A polyether oligomer having an unsaturated bond represented by the following formula: —O—CH ₂ —CH (CH ₃ ) ＝ CH _2, and a compound having a reactive silicon group, H—Si (OCH ₃ ) _{And 3} , under an atmosphere having oxygen, a catalyst, and a reactive silicon group-containing polyether oligomer having a reactive silicon group shown below obtained by reacting in a system in which a sulfur compound is present, The curable composition according to claim 1, _{-O-CH 2 -CH (CH 3} ) -CH 2 -Si (OCH 3)
_Three 5. The curable composition according to claim 4, wherein 85% or more of the terminals of the reactive silicon group-containing polyether oligomer are reactive silicon groups.