JPH11116763A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having a low viscosity which provides a cured product of a high gel content with excellent extensibility and weather resistance by compounding as indispensable components a vinyl polymer and a polyether type polymer, both components containing a crosslinkable silyl group of the same specific structure. SOLUTION: There is provided a composition containing as indispensable components a vinyl polymer having at least one crosslinkable silyl group represented by formula I, preferably a polymer with a ratio of a wt. average mol.wt. to a number average mol.wt., measured by the gel permeation chromatography, of less than 1.8 and/or a (meth)acrylic polymer, and a polyether type polymer having at least one crosslinkable silyl group represented by the formula and preferably consisting essentially of a polypropylene oxide. In the formula I, R<1> and R<2> are each a 1-20C alkyl, 6-20C aryl, 7-20C aralkyl, or a group of the formula; (R')3 SiO2 -(wherein R' is a 1-20C monovalent hydrocarbyl group); Y is a hydroxyl group or a hydrolyzable group; a is 0-3; b is 0-2; m is 0-19; and a+mb>=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition modified with a vinyl polymer having at least one crosslinkable silyl group. More specifically, the present invention relates to a curable composition excellent in high elongation after curing, weather resistance, and the like by blending with a polyether polymer having at least one crosslinkable silyl group.

[0002]

2. Description of the Related Art Polyether polymers having at least one crosslinkable silyl group are disclosed, for example, in JP-B-45-3631.
9, No. 46-12154, No. 46-30741,
JP-A-49-32673, JP-A-50-156599,
Nos. 51-73561, 54-6096, 55-
Nos. 13767, 55-13768, 55-821
No. 23, No. 55-123620, No. 55-12512
No. 1, 55-131021, 55-131022
Nos. 55-135135 and 55-137129
And JP-A-3-72527, JP-A-3-97825, and the like, and when cured, a high-elongation cured product is obtained, which is mainly used as an elastic sealing material for buildings and the like. . However, these polyethers, particularly polyethers having polypropylene oxide as a main chain, have a problem that unless an antioxidant is used, the hydrogen atom bonded to the tertiary carbon is easily oxidized and the weather resistance is deteriorated. In order to solve this problem, the present inventors have already made Japanese Patent Publication No. 2-42.
Nos. 367 and 2-44845, weather resistance is improved by blending an acrylic polymer having at least one crosslinkable silyl group with a polyether polymer having at least one crosslinkable silyl group. A curable composition was proposed. Japanese Patent Publication No. 4-69667 discloses a sealing material composition comprising a blend of an acrylic polymer having alkoxysilyl groups at both molecular terminals and a polyether polymer having alkoxysilyl groups at both molecular terminals.

[0003]

A vinyl polymer having at least one crosslinkable silyl group to be blended with a polyether polymer having at least one crosslinkable silyl group is usually a radical polymerizable polymer having a crosslinkable silyl group. Initiator,
Alternatively, it is produced using a chain transfer agent. For this reason, it is difficult to introduce a crosslinkable silyl group into both ends at a high ratio, and there is a problem that the gel content of the cured product is reduced.
On the other hand, in order to obtain a sufficient cured product gel component, it is necessary to use a monomer having a crosslinkable silyl group in combination, but in this case, the high elongation characteristic inherent in the polyether polymer is impaired. There was a problem. In this case, particularly, the elongation at break is low, so that the use of the composition is greatly limited. Therefore, when used as a sealing material, some physical properties such as an increase in modulus, a decrease in elongation, a deterioration in residual tack, and a decrease in gel content have to be sacrificed in order to improve weather resistance. Also used here (meta)
Since the acrylic polymer is synthesized by free radical polymerization, there is a problem that the molecular weight distribution is wide and the viscosity is high, and the mixture with the polyether polymer also has a high viscosity.

In the present invention, the use of a vinyl polymer having a low viscosity and a high proportion of crosslinkable silyl groups introduced therein allows the polyether polymer having crosslinkable silyl groups to have an inherently high elongation property. An object of the present invention is to provide a curable composition having a high gel content and excellent weather resistance without impairing the curability.

[0005]

According to the present invention, there is provided a curable composition comprising a vinyl polymer having at least one crosslinkable silyl group and a polyether polymer having at least one crosslinkable silyl group as essential components. The inventors have found that the above-mentioned problems can be solved, and arrived at the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (I) used in the present invention
The vinyl polymer of the component has at least one crosslinkable silyl group represented by the following general formula (1). -[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1) wherein R ¹ and R ² each have 1 to 1 carbon atoms. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, And three R's may be the same or different), and when two or more R ¹ or R ² are present, they may be the same. Well, they can be different. Y represents a hydroxyl group or a hydrolyzable group,
When two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied.加 水 The hydrolyzable group represented by Y is not particularly limited, and conventionally known groups can be used. Specifically,
Hydrogen, a halogen atom, an alkoxy group, an acyloxy group,
Ketoximate group, amino group, amide group, aminooxy group, mercapto group, alkenyloxy group and the like,
In terms of mild hydrolysis and easy handling,
Alkoxy groups are particularly preferred. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and a + mb, that is, the sum of the hydrolyzable groups is 1 to
A range of 5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one, or two or more. In the case of silicon atoms linked by a siloxane bond, the number may be up to about 20.

The monomer constituting the main chain of the vinyl polymer having at least one crosslinkable silyl group of the general formula (1) is not particularly limited, and various monomers can be used. The vinyl monomer used for producing the main chain of the vinyl polymer of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n (meth) acrylate
-N-butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n-pentyl (meth) acrylate, -n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( (Meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl,
Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth)
2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth)
2-perfluoroethyl acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) acryl (Meth) acrylic monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methyl Styrene-based monomers such as styrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyls such as vinyltrimethoxysilane and vinyltriethoxysilane Monomer; anhydrous Maleic acid, maleic acid, monoalkyl esters and dialkyl esters of maleic acid;
Fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
Maleimide monomers such as hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; vinyl monomers having a nitrile group such as acrylonitrile and methacrylonitrile; vinyl monomers having an amide group such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride; Allyl alcohol and the like can be mentioned. These may be used alone or a plurality of them may be copolymerized. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

A vinyl polymer having at least one crosslinkable silyl group of the general formula (1), which is obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers. A (meth) acrylic polymer is more preferable in terms of physical properties. The molecular weight of the vinyl polymer having at least one crosslinkable silyl group is not particularly limited, but is preferably in the range of 500 to 100,000. If the molecular weight is 500 or less, it is difficult for the vinyl polymer to exhibit its original characteristics,
If it is above, handling becomes difficult.

The molecular weight distribution of the vinyl polymer having at least one crosslinkable silyl group, that is, the weight average molecular weight (M) measured by gel permeation chromatography
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is not particularly limited. However, the molecular weight distribution is preferably narrow in order to suppress the viscosity of the curable composition to a low level, to facilitate handling, and to obtain sufficient cured physical properties. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, further preferably 1.6 or less, further preferably 1.5 or less, still more preferably 1.4 or less, and still more preferably 1. 3 or less.

The vinyl polymer having at least one crosslinkable silyl group can be obtained by various polymerization methods.
The method is not particularly limited. However, from the viewpoint of versatility and controllability of the monomer, it has a specific functional group that can be directly introduced into a crosslinkable silyl group by a radical polymerization method or converted into a crosslinkable silyl group in one or several steps of reaction. A more preferred method is to obtain a vinyl polymer and convert this specific functional group into a crosslinkable silyl group to obtain a vinyl polymer having at least one crosslinkable silyl group.

A radical polymerization method used in a method for synthesizing a vinyl polymer having a specific functional group containing a crosslinkable silyl group uses a specific functional group using an azo compound, a peroxide or the like as a polymerization initiator. Classified into a "general radical polymerization method" in which a monomer having a group is simply copolymerized with a vinyl monomer, and a "controlled radical polymerization method" in which a specific functional group can be introduced into a controlled position such as a terminal. it can.

The “general radical polymerization method” is a simple method and can be used in the present invention. However, in this method, since a monomer having a specific functional group is stochastically introduced into the polymer, it is necessary to use a considerably large amount of this monomer when trying to obtain a polymer having a high functionalization rate. On the contrary, when used in a small amount, there is a problem that the ratio of the polymer into which the specific functional group is not introduced becomes large.
In addition, since it is free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The "controlled radical polymerization method" further includes a "chain transfer agent method" in which a vinyl polymer having a functional group at a terminal is obtained by performing polymerization using a chain transfer agent having a specific functional group. The term "living radical polymerization method" can be classified into a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like. The “chain transfer agent method” can obtain a polymer having a high functionalization rate and can be used in the present invention. However, a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator can be used. It is necessary, and there are economical problems including treatment. Also, similar to the above-mentioned "general radical polymerization method", the molecular weight distribution is wide because of free radical polymerization,
There is also a problem that only a polymer having a high viscosity can be obtained.

Unlike these polymerization methods, the "living radical polymerization method" is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. It is difficult for the reaction to occur, and a polymer having a narrow molecular weight distribution (Mw / Mn
Is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Therefore, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the above specific functional group is more preferable. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but generally, the polymerization in which the terminal is inactivated and the polymerization in which the terminal is activated are performed. Pseudo-living polymerization that grows while in equilibrium is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, “Atom Transfer Radical Polymerization” using a radical scavenger such as a nitroxide compound as shown in p. 7228, an organic halide or the like as an initiator, and a transition metal complex as a catalyst (Atom Transfer Radii)
cal Polymerization: ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features of the `` radical polymerization method, '' the vinyl-based polymer having a specific functional group has halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and has a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a united product.
As this atom transfer radical polymerization method, for example, Matyj
aszewski et al., Journal of American
Chemical Society (J. Am. Chem. So
c. 1995, 117, 5614, Macromolecules 1995
Year, Volume 28, p. 7901, Science
e) 1996, vol. 272, p. 866, WO 96/30
No. 421, WO97 / 18247 or S
awamoto et al., Macromolecules (Macro)
1995, Vol. 28, p. 1721.

In the atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide compound is used as an initiator. Examples of the transition metal complex used as a catalyst for the above atom transfer radical polymerization include Group 7 of the periodic table,
A complex including a Group 8 element, a Group 9 element, a Group 10 element, or a Group 11 element as a central metal can be used. Preferred are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-
A ligand such as a polyamine such as aminoethyl) amine is added. Further, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, a bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and a bis (triphenylphosphine) complex of divalent nickel (NiCl ₂ (P
Ph ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also suitable as the catalyst.

The vinyl monomer used in the polymerization is not particularly limited, and any of those already exemplified can be suitably used. The polymerization reaction can be performed without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene;
Ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert Alcohol solvents such as -butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate.
These can be used alone or in combination of two or more. The polymerization can be carried out at a temperature in the range of 0 to 200 ° C, and preferably in the range of room temperature to 150 ° C.

The vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) can be obtained by the following method, but is not limited thereto. . As a method of synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group in a vinyl polymer having at least one alkenyl group can be prepared in the presence of a hydrosilylation catalyst. (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) by radical polymerization A method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule when synthesizing a vinyl polymer. (D) When synthesizing a vinyl polymer by radical polymerization, Method (E) using a chain transfer agent having a group: a vinyl polymer having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in the child; and the like.

The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. The synthesis method is illustrated below, but is not limited thereto. (Aa) When synthesizing a vinyl polymer by radical polymerization, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (2), for example. As a second monomer. ^{_{H 2 C = C (R 3}} ) -R 4 -R 5 -C (R 6) = CH 2 (2) ( wherein, R ³ represents a hydrogen or a methyl group, R ⁴ is -C
(O) O-, or o-, m-, shows a p- phenylene group, R ⁵ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, contain one or more ether bonds May be. R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms;
It represents an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.) There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. In particular, in the case of living radical polymerization, when a rubber-like property is expected, it is preferable to react as a second monomer at the end of the polymerization reaction or after the reaction of a predetermined monomer is completed.

(Ab) In the synthesis of a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,1 A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 9-decadiene. (Ac) Various organic metal compounds having an alkenyl group such as organic tin such as allyltributyltin and allyltrioctyltin are added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of substituting halogen by reacting.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (3) to form a halogen. How to replace. ^{M + C - (R 7)} (R 8) 9 -C (R 6) = CH 2 (3) ( wherein -R, R ⁶ are as defined above, R ^7, R ⁸ are both carbanion C ^- stable R ⁹ represents a direct bond or a C 1-10 alkyl group, or one of the above electron withdrawing groups and the other one of hydrogen or an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Represents an organic group of valence, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) The electron-withdrawing groups of R ⁷ and R ⁸ include —CO ₂ R, -C
Those having the structure of (O) R and -CN are particularly preferred.

(A-e) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. An alkenyl group-containing electrophilic compound such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. How to react.

(Af) The vinyl polymer having at least one highly reactive carbon-halogen bond may be, for example, an oxyanion or carboxy having an alkenyl group represented by the general formula (4) or (5). A method in which a halogen is substituted by reacting a rate anion. ^{_{H 2 C = C (R 6}} ) -R 10 -O - M + (4) ( wherein, R ^6, M ⁺ is the same .R ¹⁰ in the 1 to 20 carbon atoms
A divalent organic group may contain one or more ether _{bonds) H 2 C = C (R} 6) -R 11 -C (O) O of ^- M ⁺ (5) (wherein, R ⁶ , M ⁺ are the same as described above, and R ¹¹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds.

The above-mentioned method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is described in (Ea) radical polymerization in JP-A-4-132.
706, a method in which a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide, or methylene bromide is used as a chain transfer agent (chain transfer agent method).

(Eb) Atom transfer radical polymerization using an organic halide as described above as an initiator and a transition metal complex as a catalyst; and the like, but are not limited thereto. Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but the invention is not limited thereto. (Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group to react with a alkenyl group-containing halide such as allyl chloride.

(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate. (Ai) A method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine. (Aj) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst;

In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), a vinyl polymer is synthesized by a living radical polymerization method. Is preferred. The method (Ab) is more preferable because the control is easier. When an alkenyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization) using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferred to use coalescence. The method (Af) is more preferable because the control is easier.

The hydrosilane compound having a crosslinkable silyl group is not particularly limited, but a typical example is a compound represented by the general formula (6). _{^{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (6) ( ^{wherein, R 1, R 2, a} , b, m, Y is the same as above.) Among these hydrosilane compounds, in particular, the general formula (7) H-Si (R ² ) _3-a (Y) _a (7) (wherein, R ² , Y and a are the same as above) The compound having a crosslinkable group represented by the formula (1) is preferred from the viewpoint of easy availability.

When the above-mentioned hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. As the transition metal catalyst, for example, platinum alone, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid with alcohol, aldehyde, ketone, etc.
Platinum-olefin complexes and platinum (0) -divinyltetramethyldisiloxane complexes are exemplified. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ and RhC
l ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ ,
PdCl ₂ .H ₂ O, NiCl ₂ , TiCl _{4 and the} like.

The method for producing the vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) is exemplified by the following methods. However, the present invention is not limited to this. (Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (8) is used as a second monomer. As a reaction. H ₂ C ＝ C (R ³ ) —R ⁴ —R ⁵ —OH (8) (wherein R ³ , R ⁴ and R ⁵ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out as the second monomer at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer. Is preferred.

(Bb) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, for example, an alkenyl such as 10-undecenol, 5-hexenol, or allyl alcohol is used. A method of reacting alcohol. (Bc) A method of radically polymerizing a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808. (Bd) For example, JP-A-6-239912, JP-A-8-
283310. A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as shown in 283310. (Be) A method of radically polymerizing a vinyl monomer by using an excess of alcohols as described in, for example, JP-A-6-11612. (Bf) Hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method described in, for example, JP-A-4-132706. By introducing a hydroxyl group into the terminal. (Bg) A method of reacting a vinyl-based polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having a hydroxyl group as shown in the general formula (9) to replace halogen. ^{M + C - (R 7)} (R 8) -R 9 -OH (9) as the electron withdrawing group ^{(wherein, R 7, R 8, R} 9, the same is) R ^7, R ⁸ is -CO ₂ R, -C
Those having the structure of (O) R and -CN are particularly preferred.

(Bh) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. A method of reacting aldehydes or ketones later. (Bi) A vinyl polymer having at least one carbon-halogen bond having high reactivity, for example, a compound represented by the general formula (10)
Alternatively, a method in which a halogen is substituted by reacting an oxyanion or a carboxylate anion having a hydroxyl group as shown in (11). ^{HO-R 10 -O - M +} (10) ( wherein, R ¹⁰ and M ⁺ are the ^{same) HO-R 11 -C (O} ) O - M + (11) ( wherein, R ¹¹ and M ⁺ Is the same as described above).

In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as (Ba) to (Be), a vinyl polymer is synthesized by a living radical polymerization method. Is preferred. The method (Bb) is more preferable because the control is easier. When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at a terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable because the control is easier.

Examples of the compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and the like. γ-isocyanatopropyltriethoxysilane and the like can be mentioned, and if necessary, a generally known catalyst for a urethane-forming reaction can be used.

In one molecule used in the method (C), polymerizable
As a compound having both an alkenyl group and a crosslinkable silyl group
Is, for example, trimethoxysilylpropyl (meth) acryl
Rate, methyldimethoxysilylpropyl (meth) ac
Those represented by the following general formula (12), such as relates
Is mentioned. H_TwoC = C (R^Three) -R^Four-R¹²− [Si (R¹)_2-b(Y)_bO]_m-Si (R^Two) _3-a (Y)_a(12) (where R¹, R^Two, R^Three, R^Four, Y, a, b, and m are as described above.
the same. R¹²Is a direct bond or divalent having 1 to 20 carbon atoms
May contain one or more ether linkages.
No. ) A polymerizable alkenyl group and a crosslinkable silyl group are combined in one molecule.
There is no particular limitation on the timing of the reaction of the compound
For rubber-like properties in living radical polymerization
The end of the polymerization reaction or the reaction of the specified monomer.
After completion, it is preferable to react as a second monomer.
No. Crosslinkable silyl used in the chain transfer agent method (D)
Examples of the chain transfer agent having a group include Japanese Patent Publication No. 3-140.
68, crosslinkable silyl shown in JP-B-4-55444
Group-containing mercaptans, crosslinkable silyl group-containing hydrides
Rosilane and the like.

The vinyl polymer having at least one highly reactive carbon-halogen bond used in the method (E) can be obtained by the methods (Ea) to (Eb) as described above. it can. As a compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule, a compound represented by the general formula (13) can be given. ^{M + C - (R 7)} (R 8) -R 13 -C (H) (R 14) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (13) (wherein, R ¹ , R ² , R ⁷ , R ⁸ , Y, a, b, and m are the same as described above. R ¹³ is a direct bond or a group having 1 to 1 carbon atoms. R ¹⁴ may be hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein the divalent organic group may have one or more ether bonds.
An aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms is shown. ) The electron-withdrawing groups for R ⁷ and R ⁸ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred. Further, in order to obtain a vinyl polymer having at least one crosslinkable silyl group at the terminal of the molecular chain by a polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, It is preferable to use an organic halide or a sulfonyl halide compound having two or more highly reactive carbon-halogen bonds serving as a starting point as an initiator. As specific examples of them,

[0039]

Embedded image

(Wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms)
Represents an aralkyl group. C ₆ H ₄ represents a phenylene group.
n represents an integer of 0 to 20. X represents chlorine, bromine, or iodine. )

[0041]

Embedded image

(Wherein, X represents chlorine, bromine or iodine; n represents an integer of 0 to 20; C ₆ H ₄ represents a phenylene group). A vinyl polymer having at least one crosslinkable silyl group at the terminal of the molecular chain can be obtained in addition to the above. When an organic halide having a crosslinkable silyl group is used as an initiator, a vinyl polymer having a crosslinkable silyl group at one end and the other end having the structure of the general formula 2 can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into a crosslinkable silyl group-containing substituent, a vinyl polymer having a crosslinkable silyl group at both terminals can be obtained. As the conversion method, the method already described can be used.

Organic halide having a crosslinkable silyl group
Is not particularly limited, for example, general formula (14):
One having the structure shown in (15) is exemplified. R^FifteenR¹⁶C (X) -R¹⁷-R¹⁸-C (H) (R¹⁹) CH_Two− [Si (R¹)_2-b(Y)_bO]_m-Si (R^Two)_3-a(Y)_a(14) (where R¹, R^Two, A, b, m, X and Y are the same as above.
R^Fifteen, R¹⁶Is independently hydrogen or C 1-20
An alkyl group, an aryl group having 6 to 20 carbon atoms, or carbon
Aralkyl groups of the formulas 7 to 20, or mutually at the other end
Concatenated, R ¹⁷Is -C (O) O-, -C (O)-,
Alternatively, it represents an o-, m-, p-phenylene group. R¹⁸Is
1 direct bond, or a divalent organic group having 1 to 10 carbon atoms
R which may contain the above ether bond,¹⁹Is hydrogen,
Or an alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms
Represents an aryl group or an aralkyl group having 7 to 10 carbon atoms
You. ) (R^Two)_3-a(Y)_aSi- [OSi (R¹)_2-b(Y)_b]_m-CH_Two-C (H) (R ¹⁹ ) -R¹⁸-C (R^Fifteen) (X) -R¹⁷-R¹⁶ (15) (where R¹, R^Two, R^Fifteen, R¹⁶, R¹⁷, R¹⁸, R¹⁹,
a, b, m, X, and Y are the same as described above.) An organic halide having a crosslinkable silyl group is used as an initiator.
When used, one end is a crosslinkable silyl group and the other end is a halo.
To obtain a polymer,
A total of two or more identical or different functional groups
Using the compound above, cup the halogen terminals
By cross-linking, both ends are crosslinkable silyl groups
Can be obtained.

The compound having two or more identical or different functional groups capable of substituting a terminal halogen is not particularly limited, but includes polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides and the like. Is preferred. When an organic halide having an alkenyl group is used as an initiator, a polymer having an alkenyl group at one terminal and a halogen at the other terminal can be obtained. By converting the halogen at the terminal of the polymer thus obtained into an alkenyl-containing substituent, a vinyl polymer having an alkenyl group at both terminals can be obtained. By converting to a silyl group, a vinyl polymer having a crosslinkable silyl group at both terminals can be obtained.

In applications where rubber-like properties are required, at least one crosslinkable silyl group is preferably located at the end of the molecular chain, since the molecular weight between crosslinking points which greatly affects rubber elasticity can be increased. More preferably, they are all at the molecular chain terminals. Therefore, a vinyl polymer having at least one hydroxyl group, halogen or alkenyl group used for synthesizing a vinyl polymer having at least one crosslinkable silyl group has these functional groups at the terminal of the molecular chain. It is preferable that

A method for producing a vinyl polymer having at least one crosslinkable silyl group, in particular, a (meth) acrylic polymer is described in, for example, Japanese Patent Publication No. 3-14068 and Japanese Patent Publication No.
55544 and JP-A-6-219922. Since these methods use the "chain transfer agent method", these crosslinkable silyl groups are present at a relatively high ratio at the terminal. The molecular weight distribution of the resulting polymer is generally as wide as 2 or more, and there is a problem that the viscosity becomes high. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution, a low viscosity and a high proportion of a crosslinkable silyl group at a terminal, it is preferable to use a living radical polymerization method. In the invention, at least one crosslinkable silyl group as the component (II) is used.
The polyether-based polymer having one or more polyether polymers may or may not contain a urethane bond in the main chain. Preferably, the backbone polyether is essentially polypropylene oxide. If the viscosity is lower, the handleability becomes better, so that the polypropylene oxide polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less is more preferable. The crosslinkable silyl group may be the same as or different from the vinyl polymer of the component (I). The mixing ratio of the vinyl polymer (I) and the polyether polymer (II) is preferably in the range of 100/1 to 1/100 by weight, but is preferably in the range of 100/5 to 5/100. Is more preferable.

Since the curable composition of the present invention can have a low viscosity while having sufficient physical properties, it is more preferably used as a sealing material or an adhesive. In curing the vinyl polymer or polyether polymer having at least one crosslinkable silyl group of the present invention, a condensation catalyst may or may not be used. Titanate such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide and carboxylic acid ester or carboxylic acid Alternatively, a reaction product of a hydroxyl group-containing compound, an organic tin compound such as tin octylate, tin naphthenate; an organic aluminum compound such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetate Organic zirconium compounds such as sodium zirconium tetraisopropoxide and zirconium tetrabutoxide; Lead compounds; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, Guanidine, diphenylguanidine, 2,4,6
Amine compounds such as tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 or carboxylates thereof; laurylamine and tin octylate Reaction products and mixtures of amine compounds and organotin compounds such as reactants or mixtures; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction products of excess polyamine and epoxy compound; A known silane coupling agent, for example, one or more known silanol catalysts such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is preferably from 0 to 10 parts by weight based on 100 parts by weight of the total amount of the polymer having at least one crosslinkable silyl group. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing speed is slow only with this polymer.

A filler can be added for the purpose of adjusting the mechanical properties of the curable composition of the present invention. Specifically, reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon; fibrous fillers such as asbestos, glass fibers and filaments can be used. In order to obtain a cured product having high strength with these fillers, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc are mainly used. A favorable result can be obtained by adding a filler selected from white and the like in a range of 1 to 200 parts by weight based on 100 parts by weight of the total amount of the polymer having at least one crosslinkable silyl group. When it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. Total amount of polymer having at least one group is 100
A favorable result can be obtained if it is added in the range of 1 to 200 parts by weight with respect to parts by weight. These fillers may be used alone or in combination of two or more.

Further, a plasticizer can be added for adjusting physical properties and viscosity. Specifically, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate and butylbenzyl phthalate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate;
Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; polyerylene glycol, polypropylene glycol or polyethers obtained by converting these hydroxyl groups; Chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl, etc., and these can be used alone or as a mixture of two or more, but are not necessarily required. In addition, these plasticizers can be blended at the time of polymer production. The amount of the plasticizer is preferably in the range of 0 to 100 parts by weight based on 100 parts by weight of the total amount of the polymer having at least one crosslinkable silyl group. Glass itself, it has adhesive properties to ceramics other than glass, metal, etc., but it is not always necessary because it is possible to adhere to a wide range of materials by using various primers, It is preferably used to obtain stable adhesion to various adherends.

Examples of the adhesion promoter include phenolic compounds such as phenol, cresol, xylenol, resorcinol, alkylphenol, and modified phenols (for example, cashew oil-modified phenol and tall oil-modified phenol) and aldehyde compounds such as formalin and paraformaldehyde. Resol type or novolak type phenolic resin obtained by the reaction with
Epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, glycidyl ether epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A epoxy resin; alkyl titanates such as tetrabutyl titanate , Aromatic polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
Compounds having an amino group and a crosslinkable silyl group in one molecule, such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ Compounds having an epoxy group and a crosslinkable silyl group in one molecule, such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane; γ-mercaptopropyl Compounds having a mercapto group and a crosslinkable silyl group in one molecule such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanate Propyltriethoxysilane, γ-iso A compound having an isocyanate group and a crosslinkable silyl group in one molecule such as anatopropylmethyldimethoxysilane; a compound having an amino group and a crosslinkable silyl group in one molecule as described above and an epoxy group in one molecule A compound having a crosslinkable silyl group or a reaction product of a compound having an isocyanate group and a crosslinkable silyl group in one molecule; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ -(Meth) in one molecule such as (meth) acryloxypropylmethyldimethoxysilane
Reaction products of a compound having an acryloxy group and a crosslinkable silyl group and a compound having an amino group and a crosslinkable silyl group in one molecule as described above; These may be used alone or in combination of two or more. Among them, compounds having amino group and crosslinkable silyl group in one molecule, compounds having epoxy group and crosslinkable silyl group in one molecule, and mercapto group crosslinkable in one molecule, whose physical properties and adhesion are relatively easy to control Compound having a silyl group, reaction product of a compound having an amino group and a crosslinkable silyl group in one molecule and a compound having an epoxy group and a crosslinkable silyl group in one molecule, (meth) acryloxy group and a crosslinkable silyl group in one molecule A compound having at least one of nitrogen, oxygen and sulfur atoms and a crosslinkable silyl group in one molecule such as a reaction product of a compound having the compound having an amino group and a crosslinkable silyl group in one molecule Compounds are preferred. The organic group having at least one of the above-mentioned nitrogen, oxygen and sulfur atoms is an amino group, an isocyanate group or a group formed by a reaction of these groups. Compounds having an organic group having an atom and a crosslinkable silyl group are more preferred.

The adhesion promoter is used in an amount of 100 parts by weight based on the total amount of the polymer having at least one crosslinkable silyl group.
It is preferred to use from 0.01 to 20 parts by weight. 0.
At 01 parts by weight, the effect of improving the adhesiveness is hardly exhibited, and 20 parts by weight.
Exceeding the parts by weight adversely affects the physical properties of the cured product. The addition amount of the adhesion promoter is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.

A physical property modifier can be used to control the physical properties by increasing the hardness when the curable composition is cured, or reducing the hardness to extend the hardness. Examples of the physical property modifier include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycol. Alkylisopropenoxysilanes such as sildoxypropylmethyldiisopropenoxysilane; various silane coupling agents such as vinyltrimethoxysilane and vinylmethyldimethoxysilane; silicone varnishes; polysiloxanes and the like are added as necessary. You. A preferable result can be obtained by adding 0 to 20 parts by weight based on 100 parts by weight of the total amount of the polymer having at least one crosslinkable silyl group.

A curability modifier can be added to increase or decrease the curing rate of the curable composition, and a storage stability improver can be added to suppress the increase in viscosity during storage. As a curability modifier or storage stability improver,
Alcohols such as methanol and ethanol; orthoesters such as methyl orthoformate; compounds having a crosslinkable silyl group such as tetraethoxysilane, methyltrimethoxysilane and vinyltrimethoxysilane; and carboxylic acids such as 2-ethylhexanoic acid. No. A preferable result can be obtained by adding 0 to 20 parts by weight based on 100 parts by weight of the total amount of the polymer having at least one crosslinkable silyl group.

The curable composition of the present invention may further include various solvents such as toluene and methyl ethyl ketone; various silane coupling agents; various modifiers such as polysiloxane having a crosslinkable silyl group; polyamide wax, hydrogenated castor oil, Rheological property modifiers such as metal soaps; Surface property and / or weather resistance improvers such as UV-curable resins and oxygen-curable resins; Colorants such as pigments and dyes; Antioxidants, UV absorbers, and light stabilizers An additive such as a flame retardant may be optionally used.

The curable composition of the present invention can be prepared by any
Pre-mixed and stored, absorb moisture in the air after installation
Can be prepared as a one-component type that cures by
And a curing agent, filler, plastic
Ingredients such as water and water, and the ingredients and polymer composition
It can be adjusted as a two-component type that mixes things before use.
Wear. One component that is easy to handle and has few mistakes during construction
Molds are more preferred. Hereinafter, the present invention will be described based on examples.
However, the present invention is not limited to the following examples. (Synthesis example 1)Poly (acrylic acid-n-butyl) having halogen at terminal
Compound) 0.63 g of cuprous bromide (4.4 mm
ol), 0.76 g of pentamethyldiethylenetriamine
(4.4 mmol), acetonitrile 5 ml, 2,5-
1.6 g (4.4 mmol) of diethyl dibromoadipate
l), 44.7 g (349 mmol) of butyl acrylate
, And after freezing and deaeration, 7 under nitrogen atmosphere.
The reaction was performed at 0 ° C. for 7 hours. Through activated alumina column
Having a Br group at the end by removing and purifying the copper catalyst
A polymer was obtained. The number average molecular weight of the obtained polymer was determined by GPC.
Measured (mobile phase chloroform, converted to polystyrene) 10
700, molecular weight distribution 1.15.Poly (acrylic acid-n-butyl) having an alkenyl group at a terminal
Chill) synthesis Under nitrogen atmosphere, put the end obtained above in a 200 ml flask
Poly (n-butyl acrylate) having halogen 35
g, potassium pentenoate 2.2 g (16.1 mmol)
l), charged with 35 mL of DMAc, and reacted at 70 ° C for 4 hours
I let it. Unreacted potassium pentenoate and
And the generated potassium bromide is removed by water extraction purification,
A polymer having an alkenyl group at a terminal was obtained. Obtained weight
The number average molecular weight of the union was determined by GPC (mobile phase chloroform).
11300, molecular weight distribution 1.
It was 12. Also¹Polymer determined by H-NMR analysis
The number of alkenyl groups per molecule was 1.82.
Was.Poly (acrylic acid-) having a crosslinkable silyl group at a terminal
Synthesis of n-butyl) The alkenyl group at the terminal obtained above was placed in a 200 mL pressure-resistant reaction tube.
G of methyldimethoxysilane 1.8 g of a polymer having
mL (14.5 mmol) methyl orthoformate 0.26 m
L (2.4 mmol), platinum bis (divinyltetramethyl)
Rudisiloxane) 10^-Fourmmol at 100 ° C
Reaction for 4 hours, polymer having crosslinkable silyl group at terminal
I got The viscosity of the obtained polymer is 44 Pa · s,
The number average molecular weight is measured by GPC (mobile phase chloroform, polyphase).
11,900 in terms of styrene) and a molecular weight distribution of 1.12.
Was. Also¹Per H-NMR analysis per polymer molecule
The number of crosslinkable silicon groups was 1.46. (Comparative Synthesis Example 1)Crosslinkable silyl groups using crosslinkable silicon group-containing monomers
Of poly (n-butyl acrylate) having 400 g of toluene, 385 g of butyl acrylate,
15 g of methyldimethoxysilylpropyl acrylate, azobi
6 g of isobutyronitrile was bubbled with nitrogen in a 1 L flask.
Polymerization was performed at 105 ° C. for 7 hours while ringing. Toluene
By distilling off the poly (acrylic acid) having a crosslinkable silyl group,
(N-butyl lylate) was obtained. The viscosity of this polymer is
The number average molecular weight was measured by GPC (moving
850 by phase chloroform, polystyrene conversion)
0 and the molecular weight distribution was 2.47. Also¹H-NMR
Average number of hydroxyl groups per polymer determined by analysis
The number was 1.40. (Reference Synthesis Example 1)Synthesis of hydroxyl-terminated polypropylene oxide Zinc hexacyanocobaltate-glyte in autoclave
Of the complex 0.04 g and dipropylene glycol 2.0 g
A THF solution and 9.6 g of propylene oxide were added,
The reaction was performed at 76 ° C. under a nitrogen atmosphere. Then propylene
145.2 g of oxide was added to the reaction system. Unreacted mode
The product and the solvent were recovered and purified to give 150 g of an oil.
The product shows a single peak by GPC analysis and has a molecular weight distribution.
(Mw / Mn) was 1.14. Also its hydroxyl value
Was 11.8 mgKOH / g.Unsaturated group terminal
Synthesis of propylene oxide Hydroxyl-terminated polypropylene oxide 1 obtained above
20 g of a methanol solution of sodium methoxide (28 g)
wt%) of 5.8 g (30.2 mmol)
After reacting at 130 ° C for 1 hour in a clave, devolatilization under reduced pressure
did. After returning to a nitrogen atmosphere, 2.8 g of allyl chloride (3
6.2 mmol) and reacted for 2 hours. This anti
The reaction mixture is dissolved in hexane and absorbed with aluminum silicate.
Unsaturated by distilling off hexane under reduced pressure
A terminal polypropylene oxide was obtained. Synthesis of crosslinkable silyl-terminated polypropylene oxide Unsaturated group-terminated polypropylene oxy obtained by the above synthesis
Charge 120 g of the side into a pressure-resistant glass reaction vessel,
Platinic acid in isopropanol (25 g of H_TwoPtCl₆
・ 6H_TwoO was dissolved in 500 g of isopropanol
Was added and stirred for 30 minutes. Methyldime
Toxisilane (2.1 g, 20.2 mmol) was added dropwise to 9
The reaction was performed at 0 ° C. for 2 hours. By reducing the pressure, the volatile components
Removed and crosslinkable silyl-terminated polypropylene oxide
I got The viscosity of this polymer is 6 Pa · s, and the number average
The molecular weight was measured by GPC (mobile phase chloroform, polystyrene).
17300, and the molecular weight distribution was 1.14.
there were. (Examples 1 and 2) The vial having a crosslinkable silyl group of Synthesis Example 1
Having a crosslinkable silyl group according to Reference Synthesis Example 1
The polyether polymer was mixed at the ratio shown in Table 1 and the viscosity was
Was measured. For 100 parts by weight of this mixture, 1 part of water
And 1 part by weight of dibutyltin dimethoxide with stirring
Then, it was poured into a single frame having a thickness of 2 mm. Using a vacuum dryer
By degassing at room temperature and curing at 50 ° C for 3 days
A sheet of a rubber-like cured product was obtained. Gel by toluene extraction
The fraction was determined. No. 2 (1/3) from rubber-like cured product sheet
Dumbbell specimens were punched out and pulled using an autograph.
Conduct a tension test, stress at 50% elongation (M50),
The strength at break (Tb) and the elongation at break (Eb) were measured.
(200 mm / min). Small pieces from rubber-like cured product sheet
And place it in the Sunshine Weatherao Meter
Was. The state after a lapse of 60 hours was observed (accelerated weather resistance).
The results are shown in Table 1. (Comparative Examples 1 and 2) Instead of the polymer obtained in Synthesis Example 1, a ratio
Same as Examples 1 and 2 except that the polymer obtained in Comparative Synthesis Example 1 was used.
The physical properties were measured as described above. The results are shown in Table 1.
Was. Comparative Example 3 Vinyl Polymer of Synthesis Example 1 and Reference Synthesis Example 1
Instead of mixing the polyether polymer of
Except for using 100 parts by weight of the polyether polymer of Example 1,
Physical properties were measured in the same manner as in Examples 1 and 2. Combine the results
The results are shown in Table 1. (Reference Examples 1 and 2) The vinyl polymer of Synthesis Example 1 and Reference Synthesis
Instead of mixing the polyether polymer of Example 1, synthesis
The vinyl polymer of Example 1 and the vinyl polymer of Comparative Synthesis Example 1
Same as in Examples 1 and 2 except that 100 parts by weight of
The physical properties were measured. The results are shown in Table 1.

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[Table 1]

By blending the polymer of Reference Example 1 with the polymer of Reference Example 1, the weather resistance was improved. Comparative Synthesis Example 1 even though the polymer of Synthesis Example 1 had a higher number average molecular weight
And the mixed solution also has a lower viscosity than that of the polymer of Comparative Synthesis Example 1 when using the polymer of Synthesis Example 1 and has a higher gel content. Thing was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 133/06 C09D 133/06 175/08 175/08 183/12 183/12 C09K 3/10 C09K 3/10 E

Claims (11)

[Claims] 1. The following two components: (I) a vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1), and (II) a crosslinkable silyl group represented by the general formula (1). Curable composition comprising, as an essential component, a polyether polymer having at least one -[Si (R ¹ ) _2-b (Y) _b O] _m -Si (R ² ) _3-a (Y) _a (1) wherein R ¹ and R ² each have 1 to 1 carbon atoms. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, And three R's may be the same or different), and when two or more R ¹ or R ² are present, they may be the same. Well, they can be different. Y represents a hydroxyl group or a hydrolyzable group,
When two or more Ys are present, they may be the same or different. a is 0, 1, 2, or 3
And b represents 0, 1, or 2. m is 0 to 19
Is an integer. However, it is assumed that a + mb ≧ 1 is satisfied. ｝ 2. The curable composition according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight of the vinyl polymer as component (I) measured by gel permeation chromatography is less than 1.8. 3. The curable composition according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 4. The method for producing a vinyl polymer as the component (I) is a living radical polymerization method.
4. The curable composition according to any one of items 3 to 3. 5. The method for producing a vinyl polymer as the component (I) is an atom transfer radial polymerization method.
5. The curable composition according to any one of items 4 to 4. 6. The curable composition according to claim 1, which has at least one crosslinkable silyl group represented by the general formula (1) of the component (I) at a molecular chain terminal. 7. A vinyl polymer having at least one crosslinkable silyl group represented by the general formula (1) as the component (I) is prepared by the following steps: (1) Starting an organic halide or a sulfonyl halide compound. By subjecting a vinyl monomer to radical polymerization of a vinyl monomer with a catalyst and a transition metal complex as a catalyst to produce a halogen-terminated vinyl polymer, and (2) reacting an oxyanion having an alkenyl group to displace the halogen. 7. A polymer obtained by producing a vinyl polymer having an alkenyl group at a terminal and reacting with (3) a hydrosilane compound having a crosslinkable silyl group represented by the general formula (1). The curable composition according to any one of the above. 8. A vinyl polymer having a crosslinkable silyl group represented by the general formula (1) as the component (I) is obtained by the following steps: (1) polymerizing a vinyl monomer by a living radical polymerization method; Manufacture vinyl polymer,
(2) Subsequently, at least two alkenyl groups having low polymerizability
A vinyl polymer having an alkenyl group at the terminal is produced by reacting a compound having two or more groups, and the terminal alkenyl group is reacted with a hydrosilane compound having a crosslinkable silyl group represented by the general formula 1 to form a silyl group-containing substituent. Converting the polymer.
The curable composition according to any one of the above. 9. The curable composition according to claim 1, wherein the polyether polymer of the component (II) is essentially a polypropylene oxide. 10. A sealing material using the curable composition according to any one of claims 1 to 9. 11. A pressure-sensitive adhesive using the curable composition according to any one of claims 1 to 10.