JP2000327902A - Hardening composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject hardening composition giving a cured material having improved residual tackiness in the range of physical properties such as tensile property and rubber elasticity required as a composition for sealing material for general building use by including a polyether oligomer including a specific silicone including reactive group and a plasticizer. SOLUTION: A composition includes (A) 100 pts.wt. of a polyether oligomer including a specific silicone including reactive group having >=85% of the silicone including reactive groups to the whole numbers of chain terminals determined by 1H-NMR analysis and (B) 1-500 pts.wt. of a plasticizer. A group expressed by formula -[Si(R12-b)(Xb)O]mSi(R23-a)Xa (R1 and R2 are each a 1-20C alkyl, etc.; X is OH or a hydrolysable group; a is 0-3; b is 0-2; m is 0-19; with the proviso that a+Σb>=1) is preferred as the silicone including reactive group and the existence of the reactive groups on the molecular chain terminals of the component A is preferred. A filler, reinforcing material, anti-sagging agent, etc., are capably compound to the composition if necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a reactive silicon group-containing polyether oligomer and a plasticizer.

[0002]

2. Description of the Prior Art Room temperature curable compositions based on polyethers having at least one reactive silicon group in one molecule can be used, for example, as sealants for buildings, and are inexpensive and have excellent performance. I have. It is desirable that these have an appropriate curing speed upon curing, and that the rubbery cured product has a non-adhesive surface and a large elongation property as a tensile physical property and a rubber elasticity which is rich in flexibility.

[0003] A plasticizer is generally added to a room temperature curable composition not only because of the required properties such as improvement in tensile properties but also in terms of cost and workability. Depending on the composition and curing conditions, the cured product does not cure sufficiently and the residual tack (stickiness) on the surface of the cured product
Therefore, it is contaminated by the attachment of dust and the like to impair the appearance, and improvement has been desired.

The present inventors have already disclosed Japanese Patent Application Laid-Open No. 61-3406.
No. 6 and JP-A-61-34067, a monovalent silanol compound or a monovalent silanol compound is used as a method for improving the modulus, elongation characteristics and residual tack (adhesion) of a cured rubber-based organic polymer having a reactive silicon group. A simple method of adding a derivative has been proposed.

As a result, although the tensile properties of the cured product have been improved, there is still room for improvement in the residual tack (adhesion).

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cured material having an improved residual tack (low tackiness) within a range of physical properties having tensile properties and rubber elasticity required for a general sealing material composition. An object of the present invention is to provide a curable composition that gives an object.

[0007]

That is, the present invention relates to (I) a method in which the number of reactive silicon groups to the number of molecular chain terminals is ¹ H-NMR.
100 parts by weight of a reactive silicon group-containing polyether oligomer which is at least 85% by analysis, and (II) plasticizer 1
It is a curable composition containing up to 500 parts by weight.

Hereinafter, the present invention will be described in detail.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Reactive silicon group-containing polyether oligomer (I) used in the curable composition of the present invention
Means that the number of reactive silicon groups is ¹ H-
It is at least 85% by NMR analysis.

The reactive silicon group referred to in the present invention is a group having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, and a group capable of forming a siloxane bond by a mutual condensation reaction to form a crosslink. Although not particularly limited, preferred examples include a group represented by the general formula (1).

[0011] - from _{^{(Si (R 1 2-b}} ) (X b) O) m Si (R 2 3-a) X a (1) ( wherein R ¹ and R ² are the same or different C 1 -C 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO
Represents a triorganosiloxy group represented by-, and when two or more R ¹ or R ² are present, they may be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a is 0,
1, 2 or 3 represents b, and 0 represents 1, 1 or 2. Further, as to _{b in the} m number of —Si (R ¹² _-b ) (X _b ) —O— groups, they may be the same or different. m represents an integer of 0 to 19. Where a
+ Σb ≧ 1). Specific examples of R ¹ and R ² in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group,
An aralkyl group such as a benzyl group; and a triorganosiloxy group represented by (R ′) ₃ SiO— wherein R ′ is a methyl group, a phenyl group, or the like. As R ¹ , R ² and R ′, a methyl group is particularly preferred.

The hydrolyzable group in 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, a ketoximate group, an amino group, an amide group,
Examples thereof include an acid amide group, 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.

These hydroxyl groups and hydrolyzable groups can be bonded to one to three silicon atoms, and (a + Δb) is 1
To 5 is preferred. When two or more hydroxyl groups or hydrolyzable groups are present in the reactive silicon group, they may be the same or different.

The number of silicon atoms in the reactive silicon group may be one or two or more. In the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like, 20
The number may be about one.

The reactive silicon group represented by the following general formula (8) is preferable because it is easily available. _{^{-Si (R 2 3-a)}} X a (8) ( wherein R ^2, X, a is the same as the groups described by the general formula (1).) The reactive silicon group of the polyether It may be present as a side chain inside the molecular chain or at the terminal, but it is particularly preferable to be present at the terminal for applications such as sealants for buildings. When the reactive silicon group is present as a side chain inside, the effective amount of the network chain of the polyether oligomer component contained in the finally formed cured product becomes small, so that the rubber-like cured product having high elastic modulus and low elongation is obtained. Is easily obtained. On the other hand, if the reactive silicon group is present near the end of the molecular chain, the effective amount of the network chain of the polyether oligomer component contained in the finally formed cured product increases, so that the high elasticity and high elongation have a low elastic modulus. The resulting rubber-like cured product is easily obtained. In particular, when the reactive silicon group is present at the terminal of the molecular chain, the effective amount of the network chain of the polyether oligomer component contained in the finally formed cured product becomes the largest, so that the elongation property and flexibility as the tensile properties are large. It is particularly preferable for use as a sealant for buildings where it is desirable to have a rubber elasticity rich in rubber.

Various methods are conceivable for measuring such a reactive silicon group introduction ratio.
Reactive silicon group-containing polyether oligomer (I) ¹
Performed by H-NMR analysis. That is, the introduction ratio of the reactive silicon group can be calculated by determining the ratio of the number of reactive silicon groups to the number of molecular chain terminals of the polyether oligomer by ¹ H-NMR analysis.

From the viewpoint of only the curability of the curable composition, it is sufficient that the number of reactive silicon groups is at least 50% based on the number of terminals of the polyether oligomer. However, in order to improve the residual tack (adhesiveness), it is necessary that the content be 85% or more. For further improvement, 90
% Or more, and more preferably 95% or more. Particularly preferably, it is 98% or more. The curable composition containing such a polyether oligomer has a level of tensile properties and rubber elasticity required as a sealing material composition for general buildings, and has an improved residual tack compared to conventional ones, and has an adhesive property. Low cured product can be obtained. If the above value is less than 85%, the effect of low tackiness is relatively weak. Heretofore, such a relationship between the introduction rate of the reactive silicon group and the residual tack has not been known, and it has been first clarified by the present inventors' research.

The main chain structure of the reactive silicon group-containing polyether oligomer (I) may be any structure having a structure represented by —RO— as a repeating unit.
R may be a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen and carbon 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.

The main chain structure of such a reactive silicon group-containing polyether oligomer (I) can be obtained by using a dihydric alcohol, a polyhydric alcohol or various oligomers having a hydroxyl group as an initiator in the presence of various catalysts. From one to one
It is derived from the main chain structure of a hydroxy group-containing polyether oligomer obtained by subjecting a substituted or unsubstituted epoxy compound having two carbon atoms to ring-opening polymerization.

The epoxy compound is not particularly restricted but includes, for example, alkylene oxides, specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α -Methylstyrene oxide and alkyl, allyl or aryl glycidyl ethers, specifically, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether and the like. Among them, alkylene oxides are preferred. In particular, the main chain structure of the reactive silicon group-containing polyether oligomer (I) is preferably formed mainly from propylene oxide from the viewpoint of availability of raw materials, cost, and reaction control. Here, "mainly formed from propylene oxide" means that propylene oxide accounts for 50% or more, preferably 70% or more, particularly preferably 90% or more of all the repeating units of the main chain structure. What do you mean?

The initiator is not particularly restricted but includes, for example, ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol. Glycol, polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol and the like.

As the catalyst for the ring-opening polymerization, KOH, Na
Known catalysts such as alkali catalysts such as OH, acidic catalysts such as trifluoroborane-etherate, double metal cyanide complex catalysts such as aluminoporphyrin metal complex and cobalt zinc cyanide-glyme complex catalyst are used. In particular, when a double metal cyanide complex catalyst is used, since an allyl-terminated polyether oligomer component by-produced as a by-product is small, when an unsaturated group other than an allyl group is introduced, an unsaturated group other than the allyl group is introduced. It is preferable because the introduction ratio of the saturated group is improved.

The main chain structure of the reactive silicon group-containing polyether oligomer (I) is preferably one derived from a polyether oligomer obtained by ring-opening addition polymerization of an alkylene oxide in the presence of a double metal cyanide complex. preferable.

The polyether oligomer obtained by polymerization may or may not have a higher molecular weight by reacting with a polyvalent halogen compound or the like.

As a method for obtaining the reactive silicon group-containing polyether oligomer (I), for example, a hydroxy group-containing polyether oligomer is obtained by polymerization, and the hydroxy group of the polyether oligomer is converted into a specific unsaturated group. Reactive silicon group-containing polyether oligomer (A)
And hydrosilylating this terminal unsaturated group.

Specifically, (a) a molecule represented by the general formula (2): H ₂ C ＝ C (R ³ ) —R ⁴ —O— (2) (wherein R ³ has 10 or less carbon atoms) A hydrocarbon group, R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom)
Or a general formula (3): HC (R ³ ) = CH—R ⁴ —O— (3) (wherein R ³ is a hydrocarbon group having 10 or less carbon atoms, R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom)
A polyether oligomer containing at least one unsaturated group at the side chain or at the terminal and having a main chain of polyether, and (b) a reactive silicon group-containing compound,
(C) It can be obtained by reacting in the presence of a Group VIII transition metal catalyst.

Conventionally, in the hydrosilylation reaction between an unsaturated group and a compound containing a reactive silicon group, in a polyether oligomer having an allyl group as an unsaturated group, a propenyl group is generated by internal rearrangement of the allyl group as a side reaction. Therefore, the reaction yield of the reactive silicon-containing group with respect to the unsaturated group is limited. However, when a reactive silicon group-containing compound is introduced into a polyether oligomer containing an unsaturated group represented by the general formulas (2) and (3) by a hydrosilylation reaction, the reactivity which could not be obtained conventionally can be obtained. A polyether oligomer having a silicon group introduction rate of 85% or more can be obtained.

In the above general formulas (2) and (3), R
^ThreeIs, for example, a linear alkyl group such as methyl, ethyl
, Propyl, butyl, pentyl, hexyl, hepti
Octyl, nonyl, decyl, branched alkyl, e.g.
Isopropyl, isobutyl, isopentyl, isohexyl
Can represent a sil or aryl group, such as a phenyl group.
Even if it is only one kind, it is a mixture of several kinds.
May be. Further, from the viewpoint of reactivity, CH_Three-, CH_ThreeC
H_Two-Is particularly preferred, and CH_Three-Is particularly preferred. R^FourIs
At least one selected from the group consisting of hydrogen, oxygen and nitrogen
Having 1 to 20 carbon atoms as a constituent atom
For example, -CH_Two-, -C_TwoH _Four-, -C_ThreeH
₆-, -C_FourH₈-, -C_FiveH_Ten-, -C₆H_Four-, -C₆H
₁₂-, -C₇H₁₄, -C₈H₁₆-, C₉H₁₈, -C_TenH₂₀
-, -CH (CH_Three)-, -CH_Two-CH (CH_Three)-,
-CH_Two-CH (CH_Three) -CH_Two-, -C_TwoH_Four-CH
(CH_Three)-, -CH_Two-C₆H_Four-, -CH_Two-C₆H_Four−
CH_Two-, -C_TwoH_Four-C₆H_FourAnd the like. Combination
-CH because it is easy to form_Two-, -CH_TwoCH_Two-, -C
H_TwoCH (CH_Three)-Is preferred. In addition, the availability of raw materials
-CH_Two-Is particularly preferred.

Further, specific structures of such an unsaturated group include H ₂ C ＝ C (CH ₃ ) —CH ₂ —O— and H ₂ C
ＣC (CH ₂ CH ₃ ) —CH ₂ —O—, H ₂ C ＝ C (C
_{H 2 CH (CH 3))} - CH 2 -O-, HC (CH 3) =
CH—CH ₂ —O— and the like. In particular, from the viewpoint of reactivity, H ₂ C ＝ C (CH ₃ ) —CH ₂ —O—, HC
(CH ₃ ) ＝ CH—CH ₂ —O— is preferred. Further, H ₂ C ＝ C (CH ₃ )-
CH ₂ —O— is particularly preferred.

As a method for producing (a) by introducing an unsaturated group into the hydroxy-terminated polyether oligomer obtained by performing the above-mentioned ring-opening addition polymerization, a known method may be used. Examples of the method include reacting a compound having an unsaturated bond with a polyether oligomer to bond the compound with 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,-
After generating OM (M is Na or K), general formula (6): H ₂ C ＣC (R ³ ) -R ⁴ -X (6) (wherein R ³ is a hydrocarbon group having 10 or less carbon atoms) , R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom,
X is a halogen) or the general formula (7): HC (R ³ ) = CH—R ⁴ —X (7) (wherein R ³ is a hydrocarbon group having 10 or less carbon atoms, R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom,
X is a halogen) and a method of producing a polyether oligomer having an unsaturated group at a terminal by reacting the compound with an organic halogen compound represented by the formula (1).

The molecular weight of the polyether oligomer of component (a) is not particularly limited, but the number average molecular weight is 1,000.
To 100,000. If the number average molecular weight is less than 1,000, the resulting cured product of the reactive silicon group-containing polyether oligomer becomes brittle, and
If it exceeds 00, the concentration of the functional group becomes too low, the curing rate decreases, and the viscosity of the polymer becomes too high, which makes the handling difficult. Further, the number average molecular weight is preferably from 1,000 to 50,000 from the viewpoint of the viscosity of the obtained reactive silicon group-containing polyether oligomer, and from 5,000 to 50,000 in terms of mechanical properties. Particularly preferred.

Here, the number average molecular weight of the polyether oligomer is determined by directly measuring the terminal group concentration by a titration analysis based on the principle of a method for measuring a hydroxyl value according to JIS K1557 and a method for measuring an element number such as JIS K0070. And
It is defined as the number average molecular weight determined in consideration of the structure of the polyether oligomer. As a relative measurement method of the number average molecular weight, a calibration curve of the molecular weight in terms of polystyrene obtained by general GPC measurement and the above-mentioned end group molecular weight was prepared, and GP
It is also possible to convert the C molecular weight into a terminal group molecular weight.

The reactive silicon group-containing compound (b) used in the production of the reactive silicon group-containing polyether oligomer (I) includes one silicon-containing group bonded to the above-mentioned hydroxyl group or hydrolyzable group in a molecule. Or more, and one or more Si
Any compound having an —H group in the molecule may be used. Typical examples include a compound represented by the following general formula (9). _{^{H- (Si (R 1 2-}} b) (X b) O) m Si (R 2 3-a) X a (9) ( wherein ^{R 1, R 2, X,} a, b and m are the Which is the same as the group described in the general formula (1))
Halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane, 1,1,3,3-tetramethyl-1-bromodisiloxane; trimethoxysilane; Alkoxysilanes such as triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, trimethylsiloxydiethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxy Acyloxysilanes such as methylacetoxysilane and trimethylsiloxydiacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylketoki) Mate) methyl silane, bis (diethyl ketoximate) trimethylsiloxy silane, bis (methyl ethyl ketoximate) methyl silane, ketoxime silanes such as tris (acetoxy mate) silane; alkenyloxy silanes such as methyl isopropenyl oxy silane, etc. No. Of these,
Particularly, alkoxysilanes are preferable, and a methoxy group is particularly preferable among the alkoxy groups.

Further, in the present invention, the hydrolyzable group X in the obtained terminal silyl group can be converted into another hydrolyzable group Y. 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. Examples of the hydrolyzable functional group that can be converted include an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, 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 of converting to an alkoxy group, alcohols and phenols such as methanol, ethanol, 2-methoxyethanol, sec-butanol, ter-butanol and phenol;
Alkoxides such as sodium, potassium and lithium of alcohols and phenols; orthoformates such as methyl orthoformate and ethyl orthoformate; and epoxy compounds such as ethylene oxide, propylene oxide, allyl glycidyl ether, etc. A specific example is a method of reacting with. In particular, a reaction system comprising alcohols and phenols and orthoformates in combination with
If a reaction system composed of an alcohol compound and a phenol compound and an epoxy compound is used, the reaction can be easily carried out, and preferable results can be obtained.

Similarly, as a method for converting to an acyloxy group, carboxylic acids such as acetic acid and propionic acid;
Specific examples include a method of reacting an acid anhydride such as acetic anhydride, a sodium salt, a potassium salt and a lithium salt of a carboxylic acid with a halogen functional group.

Similarly, as a method for converting to an aminooxy group, N, N-dimethylhydroxylamine, N, N-
The method of reacting hydroxylamines such as diethylhydroxylamine, N, N-methylphenylhydroxylamine and N-hydroxylpyrrolidine, sodium salts, potassium salts and lithium salts of hydroxylamines; No.

Similarly, as a method for converting to an amide group,
N, N-dimethylamine, N, N-diethylamine,
Specific examples include a method of reacting primary and secondary amines such as N-methylphenylamine and pyrrolidine, sodium salts, potassium salts and lithium salts of primary and secondary amines with a halogen functional group.

Similarly, as a method for 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.

A ketoxime such as acetoxime or methyl ethyl ketoxime; a reaction system in which a mercaptan such as N-octyl mercaptan or t-butyl mercaptan is combined with an orthoformate or an epoxy compound can be used to form a ketoxime group and a mercapto group, respectively. The other portion can be converted to an alkoxyl group derived from an orthoformate or an epoxy compound.

As mentioned above, only in the case of the halogen function,
Instead of converting into other hydrolyzable functional groups, various hydrolyzable functional groups can be converted into other hydrolyzable functional groups and used.

The group VIII transition metal catalyst (c) used for producing the reactive silicon group-containing polyether oligomer (I) 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 P
tCl ₆ · 6H ₂ O, platinum - vinylsiloxane complex, a platinum - olefin complexes, Pt metal, RhCl (PP
_{h 3) 3, RhCl 3,} Rh / Al 2 O 3, RuCl 3, Ir
Cl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O,
Although compounds such as NiCl ₂ and TiCl ₄ can be used, it is particularly preferable to use either a platinum-vinylsiloxane complex or a platinum-olefin complex from the viewpoint of hydrosilylation reactivity.

The term "platinum-vinylsiloxane complex" as used herein is a generic term for compounds in which a siloxane, a polysiloxane, or a cyclic siloxane having a vinyl group in the molecule as a ligand is coordinated with a platinum atom. Specific examples of the ligand include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,3,5,7-tetramethyl-
1,3,5,7-tetravinylcyclotetrasiloxane and the like can be mentioned. Specific examples of the olefin ligand of the platinum-olefin complex include 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, and 1,5-cyclooctadiene. Among the above ligands, 1,9-decadiene is particularly preferred.
The platinum-olefin complex is described in JP-B 8-90.
06.

The amount of the catalyst used is not particularly limited, but it is usually preferable to use 10 ^-1 to 10 ^-8 mol of the platinum catalyst per mol of the 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.

The hydrosilylation reaction in the production of the reactive silicon group-containing polyether oligomer (I) is usually carried out in the following manner.
The temperature is preferably in the range of 0 to 150 ° C, preferably 20 to 120 ° C, and more preferably 40 to 100 ° C.

In the above hydrosilylation reaction, a solvent such as benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, hexane, heptane or the like may be used, if necessary, for example, to adjust the reaction temperature or the viscosity of the reaction system. Can be used.

Particularly, in the case of hydrosilylation of a polymer compound, a method using a solvent is preferred for liquefaction or viscosity reduction. The plasticizer added in the step of commercializing the polymer compound may be used as the reaction solvent.

The gas phase of the reactor used in the above hydrosilylation reaction may be made of only an inert gas such as nitrogen or helium, or may contain oxygen or the like. 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 above hydrosilylation reaction, by setting the oxygen concentration in the gas phase of the reactor to a value that avoids the explosive mixed composition, the hydrosilylation reaction can be safely promoted in the presence of oxygen. The oxygen concentration in the gas phase of the reactor can be, for example, 0.5 to 10%.

Further, in order to suppress the oxidation of the polyether oligomer, the reaction solvent, and the plasticizer in the system by the oxygen in the hydrosilylation reaction, the hydrosilylation reaction can be carried out 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
-Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert)
-Butylphenol), tetrakis methylene-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-sec-butyl-p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine and the like can also be used, but are not limited thereto.

In terms of accelerating the hydrosilylation reaction, reactivation of the catalyst by use of oxygen (Japanese Patent Laid-Open No. 8-28)
3339) or sulfur addition. Addition of sulfur contributes to a reduction in production time, a reduction in production cost, and an increase in productivity without causing a problem such as an increase in the amount of expensive platinum catalyst and an increase in the cost of removing the residual catalyst.

As the sulfur compound, simple sulfur, thiol,
Examples thereof include sulfide, sulfoxide, sulfone, and thioketone, and sulfur is particularly preferable, 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.

Regarding the amount of the sulfur compound added, for example,
Is 0.1 to 10 times the amount based on the number of moles of the metal catalyst,
Or 10 based on the number of moles of the alkenyl group.^-3From
10 ^-6Double the amount or 0.1% based on the total weight of the reaction solution.
001 to 10 ppm
it can. If the amount is small, the effect of the present invention is sufficiently achieved.
May not be possible. If the amount of sulfur compounds is too high
Problems that reduce the catalytic activity or hinder the reaction
In some cases, it is preferable to select the appropriate amount.
New

The reactive silicon group-containing polyether oligomer (I) obtainable by the above method is
The curable composition of the present invention may be used alone or in combination of two or more.

Further, a modified polyether oligomer having a reactive silicon group can be used as the component (I). A typical modified product is represented by the following general formula (10) in the presence of a polyether oligomer having a reactive silicon group.
And an acrylate monomer having an alkyl group having 1 to 8 carbon atoms and / or a methacrylate monomer having an alkyl group having 10 or more carbon atoms represented by the following general formula (11): And / or a modified product obtained by polymerizing a mixture of methacrylic acid alkyl ester monomers. The use of this modified product improves the weather resistance of the cured product of the curable resin composition. CH ₂ ＣC (R ⁵ ) (COOR ⁶ ) (10) (wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms). CH ₂ ＣC (R ⁵ ) ( (COOR ⁷ ) (11) (In the formula, R ⁵ is the same as above. R ⁷ represents an alkyl group having 10 or more carbon atoms.) As R ^{6 in the} general formula (10), for example, a methyl group,
Ethyl group, propyl group, n-butyl group, t-butyl group,
An alkyl group having 1 to 8, preferably 1 to 4, more preferably 1 to 2 carbon atoms, such as a 2-ethylhexyl group, can be mentioned. The monomer represented by the general formula (10) may be one type, or two or more types.

As R ^{7 in the} general formula (11), for example, lauryl group, tridecyl group, cetyl group, stearyl group, biphenyl group, etc.
30, preferably 10 to 20 long-chain alkyl groups. The monomer represented by the general formula (11) may be one type, or two or more types.

The mixing ratio of the monomer of the formula (10) to the monomer of the formula (11) is preferably from 95: 5 to 40:60 by weight, more preferably from 90:10 to 60:40.

In the polymerization, a monomer other than the formulas (10) and (11) may be used in combination. Examples of such a monomer include acrylic acid such as acrylic acid and methacrylic acid, acrylamide, methacrylamide, and N -Methylol acrylamide, amide groups such as N-methylol methacrylamide, glycidyl acrylate, epoxy groups such as glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, monomers containing amino groups such as aminoethyl vinyl ether and acrylonitrile, styrene, α-methylstyrene, Examples include monomers such as alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, and ethylene. In this case, the polymerized formula (10) and the formula (1)
It is preferable that the total of the monomers 1) is 50% by weight or more, particularly 70% by weight or more of the whole of the polymerized monomers.

In the curable composition of the present invention, (I
As the plasticizer of component (I), phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate may be used in accordance with the purpose of controlling physical properties and properties. Acid esters: dioctyl adipate,
Non-aromatic dibasic acid esters such as dioctyl sebacate; polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; chloride paraffins; Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; polymeric plasticizers; high-viscosity plasticizers and the like are used. Preferably, a high molecular weight plasticizer and / or a high viscosity plasticizer is used.

Specific examples of such a high-molecular plasticizer include, for example, polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; polyethers such as polypropylene glycol and derivatives thereof;
Polystyrenes such as methylstyrene and polystyrene;
Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene,
Examples thereof include hydrogenated polybutene, but are not limited thereto. Among these, polyester plasticizers, polyethers, polystyrenes, polybutadienes, polybutenes and the like, particularly polyethers, have good compatibility with the polyether oligomer (a). It is preferable from the point of being excellent.
The number average molecular weight of the polymer plasticizer is 5,000 to 25.0.
00, even 700-20,000, especially 4,0
00-15,000 are preferred.

Among them, the polyethers have good compatibility with the polyether oligomer (A), are excellent in the effect of lowering the viscosity, and are more effective in lowering the elastic modulus and elongation of the cured product. preferable. Among the polyethers, those having a number average molecular weight of 4,500 or more are preferable,
Those of 5,000 to 15,000 are particularly preferred.

Further, those having a small number of molecular terminals or having a small number of hydrogen groups at the molecular terminals are preferred from the viewpoint of improving the drying property of the coated alkyd paint, and those having substantially no hydroxyl group at the molecular terminals. More preferred. For the same reason, those having a terminal at an alkyl ether group, an allyl ether group, an aryl ether group or the like are more preferable.

Specific examples of such polyethers include, for example, polyoxypropylene glycol having a number average molecular weight of 4,000 or more and having a narrow molecular weight distribution or a small content of 1,000 or less. One end of propylene glycol, preferably both ends having a hydroxyl group blocked by an alkyl ether bond, alkyl phenyl ether bond, alkenyl ether bond, allyl ether bond, etc., urethane bond, ester bond, urea bond, amide bond, carbonate bond Such as those in which a hydroxyl group is blocked by a group such as an alkyl group, an aryl group, or an alkenyl group by a bond such as
It is not limited to these.

The high-viscosity plasticizer has a viscosity of 0.8 P at 25 ° C.
The molecular weight is not particularly limited as long as it is at least about a · s, preferably about 2 to 30 Pa · s. However, since the viscosity generally increases as the molecular weight increases, most of the high-molecular plasticizers usually have a high molecular weight. Also acts as a viscosity plasticizer. Specific examples of the high-viscosity plasticizer other than the high-molecular plasticizer include, for example, triaryldieethane, a mixture of isomers thereof, 1-phenyl-1-xylylethane, and chlorinated paraffin, but are not limited thereto. is not.

In the present invention, as a plasticizer other than the specific polymer plasticizer, triaryldieethane and its isomer mixture and 1
A plasticizer having a viscosity at 25 ° C of 2 Pa · s or more selected from the group consisting of -phenyl-1-xylylethane is used. Of these, triaryldieethane, a mixture of isomers thereof, and the like are preferable.

The above plasticizers may be used alone or in combination of two or more. In addition, these plasticizers may be blended as a solvent or the like during the production of the polyether oligomer (a).

The amount of the polymer plasticizer used is 1 to 500 parts by weight, preferably 10 to 450 parts by weight, particularly preferably 50 to 400 parts by weight, based on 100 parts by weight of the polyether oligomer (I). Department. If the amount is less than 1 part by weight, the effect of using a plasticizer will not be exhibited, and if it exceeds 500 parts by weight, insufficient mechanical strength of the cured product and contamination of the plasticizer by bleeding may occur.

The curable composition of the present invention may contain white carbon, carbon black, calcium carbonate,
Adhesives and adhesives can be obtained by mixing reinforcing or non-reinforcing fillers such as titanium oxide, talc, asbestos, and glass fibers, and various additives such as antioxidants, ultraviolet absorbers, pigments, and flame retardants. It can be usefully used as an agent, a paint, a sealant composition, a waterproofing agent, a spraying material, a molding material, a cast rubber material, and the like. Among them, application to a sealing material composition is particularly useful. When the curable composition of the present invention is used for a sealing material composition, a filler, a reinforcing agent, an anti-sagging agent, a coloring agent, an anti-aging agent, an adhesion promoter, a curing catalyst, a physical property adjustment, if necessary. And the like.

As fillers and reinforcing materials, heavy and light calcium carbonate; calcium carbonate surface-treated with fatty acids, resin acids, cationic surfactants, anionic surfactants, etc .; magnesium carbonate; talc; Titanium;
Barium sulfate; alumina; metal powders such as aluminum, zinc, and iron; bentonite; kaolin clay; fumed silica; quartz powder; In particular, if a filler or reinforcing material that gives transparency such as fumed silica is used, a sealing material having excellent transparency can be produced.

As the anti-dripping agent, hydrogenated castor oil derivatives;
Calcium stearate, aluminum stearate,
Examples thereof include metal soaps such as barium stearate, but they may not be necessary depending on the purpose of use or the blending of fillers and reinforcing materials.

As the coloring agent, if necessary, ordinary inorganic pigments, organic pigments, dyes and the like can be used.

Examples of the physical property modifier include various silane coupling agents, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane , Γ
Alkylisopropenoxysilanes such as glycidoxypropylmethyldiisopropenoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrisilane Methoxysilane, N
-Alkoxysilanes having a functional group such as-(β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; Is added. By using the physical property modifier, the hardness of the composition of the present invention when it is cured can be increased, or the hardness can be reduced and elongation can be obtained.

As the adhesion promoter, the polymer itself according to the present invention has adhesiveness to glass, ceramics other than glass, metal and the like, and can be adhered to a wide range of materials by using various primers. Although it is not always necessary, by using one kind or two or more kinds of epoxy resins, phenolic resins, various silane coupling agents, alkyl titanates, aromatic polyisocyanates, etc., even more types of adherends can be obtained. Adhesion can be improved.

As the curing catalyst, titanium esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate,
Organotin compounds such as dibutyltin diacetate, tin octylate, tin naphthenate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine , Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo ( Amine compounds such as 5,4,6) undecene-7 (DBU) or salts thereof such as carboxylic acids; low molecular weight obtained from excess polyamine and polybasic acid A reaction product of an excess polyamine and an epoxy compound; known silane coupling agents having an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; One or more silanol condensation catalysts may be used as needed.

A solvent may be added for the purpose of improving workability, lowering the viscosity, etc., for example, aromatic hydrocarbon solvents such as toluene and xylene, ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate and the like. And a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. These solvents may be used during the production of the polymer.

The antioxidant does not need to be particularly added, but ordinary antioxidants and ultraviolet absorbers may be used.

Such a curable composition may be prepared as a one-component type in which all the components are premixed, sealed and stored, and cured by the moisture in the air after application. Alternatively, a curing catalyst and a filler may be separately used as a curing agent. Ingredients such as plasticizer, water, etc. may be preliminarily compounded, and the compounding agent (material) and the polymer composition may be mixed as a two-component type before use. When the sealing agent composition is a one-component type, all the components are preliminarily compounded. Therefore, the water-containing components are dehydrated and dried before use, or dehydrated by decompression or the like during mixing and kneading. Is preferred.

When the curable composition is of a two-component type, there is no need to mix a curing catalyst with the main component containing the polymer, so that gelling may occur even if the compounding agent contains a small amount of water. However, when long-term storage stability is required, dehydration drying is preferred.

As a dehydration and drying method, a heating and drying method is preferable for a solid substance such as a powder, and a dehydration method using a vacuum zeolite, activated alumina, silica gel or the like is preferable for a liquid substance. is there. Alternatively, a small amount of an isocyanate compound may be blended to cause the isocyanate group to react with water for dehydration.

In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycol By adding an alkoxysilane compound such as sildoxypropyltrimethoxysilane, the storage stability is further improved.

The object of the present invention is to obtain a curable composition having an improved residual tack (adhesiveness) within the range of physical properties having tensile properties and rubber elasticity required as a general sealing material composition for buildings. The range of physical properties having tensile properties and rubber elasticity required as a sealing material composition for general buildings means that the cured product has a modulus at 50% elongation of 0.5%.
It is preferable that the relation of 05 MPa ≦ M50 ≦ 0.30 MPa is satisfied.

The modulus of the cured product at 50% elongation is 0.
If the pressure is less than 05 MPa, the displacement may follow the small displacement of the member, which is not preferable in terms of fixing the member, and the modulus of the cured product at 50% elongation is 0.30M.
When it exceeds Pa, the followability to the displacement of the member is poor,
Destruction (separation of the sealing material) at the interface between the member and the sealing material may easily occur, which is not preferable.

Here, the modulus at the time of 50% elongation of the cured product refers to a filler, a reinforcing agent, a filler, a reinforcing agent, and a curable composition comprising (I) a reactive silicon-containing polyether oligomer and (II) a plasticizer. Using a sealing material composition obtained by blending anti-sagging agents, coloring agents, anti-aging agents, light stabilizers, adhesion promoters, curing catalysts, physical property modifiers, surface modifiers, dehydrating agents, etc. as necessary. 3 days at 23 ° C and 55% humidity
After curing at 50 ° C. for 4 days, a cured product sheet having a thickness of about 3 mm was prepared, a No. 3 dumbbell in accordance with JIS-K6301 was punched out, and a tensile test was performed (tensile speed: 2).
(00 mm / min), and the tensile strength at 50% elongation at this time is defined as the modulus at 50% elongation.

[0085]

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) Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene glycol as an initiator, and the number average molecular weight was 10,000.
Thus, a hydroxyl-terminated polyether oligomer of No. 00 was obtained. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl groups of the hydroxyl group-terminated polyether oligomer was added to distill off methanol, and 3-chloro-2-methyl-1-propene was further added to terminate the terminal group. Was converted to a methallyl group. 500 g of the oligomer obtained after the desalting and purification treatment was carried out with 2,6-di-t as an antioxidant.
tert-Butyl-p-cresol and hexane as an azeotropic solvent were added, and azeotropic dehydration was performed 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 wt% toluene solution) and 56 μl of a platinum divinyldisiloxane complex (3 wt% xylene solution in terms of platinum) were added thereto, and 24.2 g of DMS (dimethoxymethylsilane) was slowly added with stirring. Was dropped. After reacting at 90 ° C. for 5 hours, unreacted DMS was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene polymer. From the ¹ H-NMR analysis of the obtained polymer,
It was confirmed that the reactive silicon group introduction rate to the terminal was 98% (polymer A). (Synthesis Example 2) Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene glycol as an initiator, and the number average molecular weight was 10,000.
Thus, a hydroxyl-terminated polyether oligomer of No. 00 was obtained. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of the hydroxyl-terminated polyether oligomer was added to distill off methanol, and 3-chloro-1-propene was further added to terminate the terminal hydroxyl group with allyl. Converted to base. Next, 2,6-di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent were added to 2,000 g of the obtained oligomer, and azeotropic dehydration was performed at 90 ° C., and hexane was distilled off under reduced pressure. After that, the atmosphere was replaced with nitrogen. 160 μl of a chloroplatinic acid catalyst (5% by weight of isopropanol solution) was added thereto, and 26.28 g of DMS (dimethoxymethylsilane) was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted DMS was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene polymer. ¹ H-N of the obtained polymer
According to the MR analysis, the introduction ratio of the reactive silicon group into the terminal was 55%.
(Polymer B). (Synthesis Example 3) Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene glycol as an initiator, and the number average molecular weight was 10,000.
Thus, a hydroxyl-terminated polyether oligomer of No. 00 was obtained. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of the hydroxyl-terminated polyether oligomer was added to distill off methanol, and 3-chloro-1-propene was further added to terminate the terminal hydroxyl group with allyl. Converted to base. Next, 500 g of the obtained oligomer was subjected to azeotropic dehydration at 90 ° C. by adding 2,6-di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent,
Hexane was distilled off under reduced pressure, followed by nitrogen replacement. To this, 40 μl of a chloroplatinic acid catalyst (5% by weight of isopropanol solution) was added, and 7.7 g of DMS (dimethoxymethylsilane) was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted DM
S was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene polymer. From the ¹ H-NMR analysis of the obtained polymer, it was confirmed that the reactive silicon group introduction rate to the terminal was 62% (polymer C). (Example 1) A curable composition was prepared with the composition shown in Table 1 (each composition is shown in parts by weight) with respect to 50 parts by weight of polymer A, and the following measurement was performed. (Example 2) The procedure of Example 1 was repeated except that a curable composition having the composition shown in Table 1 was prepared with respect to 40 parts of the polymer A. (Example 3) The procedure of Example 1 was repeated except that a curable composition having the composition shown in Table 1 was prepared with respect to 30 parts of the polymer A. Example 4 The procedure of Example 1 was repeated except that a curable composition having the composition shown in Table 1 was prepared for 40 parts of the polymer A. Comparative Example 1 The procedure was the same as in Example 1 except that 100 parts of polymer B was used. (Comparative Example 2) Same as Example 1 except that 100 parts of polymer C was used.

[0086]

[Table 1] (1) Tensile properties of cured product The curable composition is cured at a thickness of 3 mm (23 ° C. × 3 days +
(50 ° C. × 4 days), a No. 3 dumbbell of JIS K 6301 was punched out, and a tensile test was performed at a tensile speed of 200 mm / min. (2) Residual tack The curable composition was placed in an ointment can (4.5 mm deep, 46 m in diameter)
m), and cured at 23 ° C. and 55% humidity, and the degree of stickiness on the surface of the curable composition was evaluated by a finger touch method.
Evaluation was (good)> ◎, ◎, ○-◎, ○, ○ △, △, △
×, × (bad) was evaluated on an eight-point scale.

Table 2 shows the results.

[0088]

[Table 2] Example 3 is superior to Comparative Example 1 in the residual tack even though the modulus is the same as that of Comparative Example 1. The same applies to the comparison between Example 4 and Comparative Example 2. Furthermore, Example 2 is superior to Comparative Example 2 in terms of residual tack, although the modulus is smaller than Comparative Example 2.

[0089]

The curable composition of the present invention has a reduced tackiness and a reduced tackiness in the range of physical properties having tensile properties and rubber elasticity required for the above-mentioned sealing material composition for general buildings. Can be given.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Iwakiri 2-9-4 Migatadai, Nishi-ku, Kobe City, Hyogo Prefecture (72) Inventor Fumio Kawakubo 5--21-17 Kita-Ochiai, Suma-ku, Kobe City, Hyogo Prefecture

Claims (12)

[Claims] (1) 100 parts by weight of a reactive silicon group-containing polyether oligomer in which the number of reactive silicon groups relative to the number of molecular chain terminals is 85% or more by ¹ H-NMR analysis, and (II) plasticizer 1 A curable composition containing up to 500 parts by weight. 2. The curable composition according to claim 1, wherein the cured product has a modulus at 50% elongation of 0.05 MPa ≦ M50 ≦ 0.30 MPa. 3. The curable composition according to claim 1, wherein the reactive silicon group is present at a molecular chain end of the reactive silicon group-containing polyether oligomer (I). 4. The reactive silicon group is general formula (1): - (Si ( R 1 2-b) (X b) O) m Si (R 2 3-a) X a (1) ( wherein R ¹ and R ² are the same or different and are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO
Represents a triorganosiloxy group represented by-, and when two or more R ¹ or R ² are present, they may be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a is 0,
1, 2 or 3 represents b, and 0 represents 1, 1 or 2. Further, as to _{b in the} m number of —Si (R ¹² _-b ) (X _b ) —O— groups, they may be the same or different. m represents an integer of 0 to 19. Where a
+ Σb ≧ 1), the curable resin composition according to any one of claims 1 to 3. 5. The reactive silicon group-containing polyether oligomer (I) is derived from a polyether oligomer obtained by ring-opening addition polymerization of an alkylene oxide in the presence of a double metal cyanide complex catalyst. 3. The curable composition according to item 1. 6. The curable composition according to claim 1, wherein the main chain of the reactive silicon group-containing polyether oligomer (I) is mainly formed from polypropylene oxide. 7. The reactive silicon group-containing polyether oligomer (I) contains (a) a molecule represented by the following general formula (2): H ₂ C ＝ C (R ³ ) —R ⁴ —O— (2) ( In the formula, R ³ is a hydrocarbon group having 10 or less carbon atoms, R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom)
Or a general formula (3): HC (R ³ ) = CH—R ⁴ —O— (3) (wherein R ³ is a hydrocarbon group having 10 or less carbon atoms, R ⁴ is hydrogen,
A divalent organic group having 1 to 20 carbon atoms and containing at least one selected from the group consisting of oxygen and nitrogen as a constituent atom)
A polyether oligomer containing at least one unsaturated group at the side chain or at the terminal and having a main chain of polyether, and (b) a reactive silicon group-containing compound,
The curable resin composition according to any one of claims 1 to 6, wherein (c) the reaction is carried out in the presence of a Group VIII transition metal catalyst. 8. The group VIII transition metal catalyst (c) is platinum-
The curable composition according to claim 7, wherein the curable composition is at least one selected from the group consisting of a vinylsiloxane complex and a platinum-olefin complex. 9. In the general formulas (2) and (3), R
³ is CH ₃ or claim 7 or 8 curable composition, wherein the is either CH ₂ CH _3. 10. The unsaturated group represented by the general formula (2) is represented by the following general formula (4): H ₂ C ＝ C (CH ₃ ) —CH ₂ —O— (4) The curable composition according to claim 9, wherein 11. The method according to claim 1, wherein the unsaturated group represented by the general formula (3) is represented by the following general formula (5): HC (CH ₃ ) = CH—CH ₂ —O— (5) Item 10. The curable resin composition according to Item 9. 12. The curable composition according to claim 1, wherein the plasticizer (II) is a polymer plasticizer and / or a high-viscosity plasticizer.