JP2000034391A - Room temperature curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having curability, especially capable of shortening a time required to attain the development of adhesiveness by including an organic polymer containing a specific reactive end group and an epoxy resin as essential components. SOLUTION: This composition comprises (A) a polymer containing a hydrolyzable silicon group of the formula (R1 is a 1-20C monofunctional organic group; X is a hydroxyl group or a hydrolyzable group; (a) is 1, 2 or 3) in which the polymer is partially or wholly a polymer containing a group in which (a) is 3 in the formula and (B) an epoxy resin as essential components. The component A has preferably 8,000-50,000 molecular weight. The component A is preferably a polyoxyalkylene polymer having a molecular weight distribution Mw/Mn of <=1.7, containing the hydrolyzable silicon group of the formula. The ratio of the component B used is in the ratio of A/B of preferably 100/1 to 100/300 by weight. Consequently excellent adhesiveness to various substrates can be exhibited in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a room temperature curable composition which gives a cured product having a short time to develop adhesion and excellent adhesion to various substrates.

2. Description of the Related Art A polyoxyalkylene polymer having a hydrolyzable silicon group at a terminal is used for applications such as a coating composition and a sealing composition by making use of a characteristic that a cured product has rubber elasticity.

The method of curing various polymers having a hydrolyzable silicon group at the terminal and using them for sealants, adhesives, etc. is well known and is an industrially useful method. . As such a polymer and a composition using the same, JP-B-61-18570 and JP-B-61-18852 disclose a hydrolyzable silicon-group-containing polymer in which two hydrolyzable groups are bonded to one silicon atom. A curable composition using a low-molecular-weight polymer having a combined molecular weight of 15,000 or less is described. However, the cured product obtained by curing such a composition is insufficient in elongation and strength, and in particular, in the case of a one-part curable composition that cures in the presence of moisture in the air, the curability of the deep part is poor. There was a disadvantage that was significantly inferior. Further, a compound having a similar terminal hydrolyzable silicon group, having a high molecular weight and a molecular weight distribution M _w / M
_A polymer in which _n is very close to 1 and a curable composition using the same are disclosed in JP-A-3-72527 and JP-A-4-2832.
58, etc., in this case, the elongation of the cured product,
Although the strength and curability have been improved, the curability has not yet been sufficient, especially when it is desired to cure rapidly to obtain a cured product. Further, as compared with a silicon group in which two hydrolyzable groups are bonded per silicon atom,
A silicon group to which three hydrolyzable groups are bonded each has a higher hydrolysis rate, and it is expected that a polymer having such a terminal has a higher curing rate. Examples of such a polymer include JP-B-58-10418 and JP-B-58-108.
No. 10430 describes a polymer having a hydrolyzable silicon group in which three hydrolyzable groups are bonded to one silicon atom, and having a low molecular weight of 6000 or less. Although the curing speed of such a polymer is indeed faster, the internal curability, especially at low temperatures,
The elongation and flexibility of the cured product were not sufficient. Also,
These polymers have the disadvantage of low adhesive strength, and their adhesiveness is insufficient, especially when used for adhesives.
On the other hand, as a method of improving the adhesion, Japanese Patent Publication No. 2-357
No. 93 discloses a method in which a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable silicon groups per silicon atom and an acrylic polymer are used in combination.
-268720 and JP-A-7-2828 propose a method in which a polymer having a hydrolyzable silicon group and an epoxy resin are used in combination. Although such a method has the effect of improving the strength and adhesive strength of the cured product, it is still insufficient in terms of curing speed, and particularly when used as an adhesive, it is expected that the adhesiveness will be developed in as short a time as possible. Was rare.

SUMMARY OF THE INVENTION The present invention provides a method for producing
Curable, especially adhesive, using an organic polymer with terminal groups
Room temperature curable compositions with reduced time to onset
The present invention relates to the following invention. Water represented by the following formula (1)
A polymer having a decomposable silicon group, a part of the polymer
Or all hydrolyzable silicon of formula (1) wherein a is 3
Polymer (A) which is a polymer having a group, and epoxy
A room temperature curable composition containing the resin (B) as an essential component. -SiX_a R¹ _3-a ... (1) (In the formula (1), R is substituted or unsubstituted having 1 to 20 carbon atoms.)
X is a hydroxyl group or a hydrolyzable group, and a is
1, 2 or 3 is indicated. Where R¹ Exists multiple times
Sometimes, those R¹ May be the same or different, and X is
When two or more exist, their Xs are the same but different
Is also good. (Polymer (A)) In the present invention, the main chain of the polymer (A)
As polyoxyalkylene, polyester, poly
Carbonate, polyolefin, etc.
In particular, the main chain is composed of polyoxyalkylene.
preferable. Hereinafter, the main chain of the polymer (A) is polyoxy
Polymers that are alkylene (hereinafter referred to as polyoxyalkylene
The polymer (C) will be described as a representative. (Polyoxyalkylene polymer (C)) represented by formula (1)
Polyoxyalkylene having a hydrolyzable silicon group
The polymer (C) is described in, for example, JP-A-3-47825,
Proposed in Japanese Unexamined Patent Publication No. Hei 3-72527 and Japanese Unexamined Patent Publication No. Hei 3-79627.
ing. The polyoxyalkylene polymer (C) is described below.
As shown, polyoxyalkylene polymerization with functional groups
From the body, with or without organic groups at its ends
It is preferable that the compound is produced by introducing a hydrolyzable silicon group
Good. As raw material polyoxyalkylene polymer,
In the presence of a solvent and the presence of an initiator,
Hydroxyl-terminated ones prepared accordingly are preferred. start
As an agent, a hydroxy compound having one or more hydroxyl groups
Etc. can be used. Ethylene oxide as the cyclic ether
Sid, propylene oxide, butylene oxide, hex
Examples include lenoxide, tetrahydrofuran and the like. Touch
Examples of the medium include potassium compounds and cesium compounds.
Alkali metal catalyst, double metal cyanide complex catalyst, metal
Porphyrin catalysts and the like. In the present invention
Has a molecular weight of 80 as a raw material polyoxyalkylene polymer.
Polyoxyalkylene polymer having a high molecular weight of
It is preferred to use coalescence. Therefore alkaline touch
Relatively low molecular weight polyoxyl
Polyalkylene compounds such as methylene chloride on rubylene polymer
Polyoxygenated by reacting
Using an alkylene polymer or double metal cyanide complex catalyst
Using a polyoxyalkylene polymer prepared by
Is preferred. In particular, the weight average molecular weight (M_w ) and
Number average molecular weight (M_n ) Ratio M_w / M _n Is less than 1.7
It is preferable to use a lioxyalkylene polymer,
M_w/ M_n Is more preferably 1.6 or less,
M_w / M_n Is particularly preferably 1.5 or less. Book
Polyoxyalkylene having a hydrolyzable silicon group according to the invention
The polymer (C) is obtained by such polyoxyalkylene polymerization.
Of the hydrolyzable silica
It is obtained by making a base group. Raw material polyoxyal
M of kylene polymer_w / M_n The smaller the
Having a hydrolyzable silicon group obtained by
When the alkylene polymer (C) is cured, the elastic modulus is the same
Even if the cured product has large elongation and high strength,
Body viscosity is reduced and workability is excellent. Such polio
Among xyalkylene polymers, especially complex metal cyanide
Complex in the presence of an initiator,
Particularly, those obtained by polymerizing
Hydrolysis by modifying the terminal of a suitable alkylene oxide polymer
Most preferred are those having a crystalline silicon group. Composite metal cyanide
The main compound is zinc hexacyanocobaltate.
Are preferred, especially ether and / or
Or an alcohol complex. Its composition is inherently unique
Those described in JP-B-46-27250 can be used.
You. In this case, the ether is ethylene glycol di
Methyl ether (glyme), diethylene glycol di
Methyl ether (diglyme) and the like are preferable, and
Glyme is particularly preferred in terms of handling during fabrication. Al
As the coal, t-butanol is preferable. Raw polio
The number of functional groups of the xyalkylene polymer is preferably 2 or more.
If you want to increase flexibility as a cured product,
The number of functional groups of the lioxyalkylene polymer is preferably 2 or 3.
Preferred. Raw materials for obtaining good adhesion and curability
The polyoxyalkylene polymer preferably has 3 to 8 functional groups.
preferable. As the raw material polyoxyalkylene polymer,
Specifically, polyoxyethylene, polyoxypropylene
, Polyoxybutylene, polyoxyhexylene, poly
Of oxytetramethylene and two or more cyclic ethers
And copolymers. Particularly preferred raw material polyoxya
The alkylene polymer is a di- to hexavalent polyoxypropylene poly
All, especially polyoxypropylene diol
Lioxypropylene triol. Also,
When used in the methods (a) and (d), allyl-terminated polio
Olefin-terminated poly such as xylene
Oxyalkylene polymers can also be used. The polyoxya
The alkylene polymer (C) is located at the terminal or side chain of the molecular chain.
It has a hydrolyzable silicon group represented by the formula (1). -SiX_a R¹ _3-a... (1) (in the formula (1), R¹ R¹ Is a substituent having 1 to 20 carbon atoms or
X is an unsubstituted monovalent organic group, and X represents a hydroxyl group or
A is 1, 2 or 3; Where R
¹ When there are a plurality of¹ Are the same but different
And when there are a plurality of Xs, those Xs are the same.
It may be the same or different. ) Hydrolysis represented by formula (1)
The reactive silicon group is usually linked to the raw material polyoxya via an organic group.
Introduced into the alkylene polymer. That is, polyoxya
The alkylene polymer (C) has a group represented by the formula (2)
Is preferred. -R⁰ -SiX_a R¹ _3-a... (2) (in the formula (2), R⁰ Is a divalent organic group, R¹ , X, a are above
Same as above. R in formulas (1) and (2)¹ Is a substituent having 1 to 20 carbon atoms or
An unsubstituted monovalent organic group, preferably having 8 or less carbon atoms
An alkyl group, a phenyl group or a fluoroalkyl group
Yes, particularly preferably methyl group, ethyl group, propyl
Group, butyl group, hexyl group, cyclohexyl group, phenyl
And the like. R¹ When there are a plurality of
¹ May be the same or different. Hydrolyzable group for X
Are, for example, halogen atom, alkoxy group, acyl group
Luoxy, alkenyloxy, carbamoyl,
Mino group, aminooxy group, ketoxime group, hydride
And the like. Of these, those with carbon atoms
The number of carbon atoms in the water-decomposable group is preferably 6 or less, particularly preferably 4 or less.
preferable. Preferred X is alkoxy having 4 or less carbon atoms.
Si and alkenyloxy, especially methoxy, ethoxy
Group, propoxy group or propenyloxy group.
You. When there are a plurality of Xs, the Xs are the same.
May also be different. a is 1, 2 or 3. Polymer
The number of hydrolyzable silicon groups in one molecule is preferably 1 to 8.
And 2 to 6 are particularly preferred. Raw material polyoxyalkylene
The method of introducing a hydrolyzable silicon group into a polymer is particularly limited.
Although not specified, for example, by the following methods (a) to (d)
Can be introduced. (A) Powder of polyoxyalkylene polymer having hydroxyl group
After introducing an olefin group at the end, it is represented by the formula (3)
A method of reacting a hydrosilyl compound. HSix_a R¹ _3-a ... (3) (in the formula (3), R¹ , X and a are the same as above. ) Methods for introducing olefin groups include unsaturated groups and
The compound having a functional group is replaced with a polyoxya compound having a hydroxyl group.
It reacts with the terminal hydroxyl group of the alkylene polymer to form an ether bond.
Bond, ester bond, urethane bond or carbonate bond
For example, a method of binding by combination or the like can be used. Alkylene
When polymerizing oxides, allyl glycidyl ether
Copolymerization by adding any olefin group-containing epoxy compound
To the side of the raw material polyoxyalkylene polymer
Methods for introducing olefin groups into the chain can also be used. Also,
When reacting the hydrosilyl compound, a platinum-based catalyst,
Rhodium-based catalyst, cobalt-based catalyst, palladium-based catalyst,
A catalyst such as a nickel-based catalyst can be used. Chloroplatinic acid,
Platinum, such as platinum metal, platinum chloride, and platinum olefin complex
Catalysts are preferred. Also, the hydrosilyl compound is reacted
Reaction is performed at 30 to 150 ° C, preferably 60 to 120 ° C.
It is preferable to carry out at a temperature of several hours. (B) Powder of polyoxyalkylene polymer having hydroxyl group
A method of reacting a compound represented by the formula (4) at one end. R¹ _3-a-SiX_a -R^Two NCO (4) (in the formula (4), R¹ , X and a are the same as above. R^Two Is carbon
A divalent hydrocarbon group of the formulas 1 to 17; In the above reaction, a known urethanation catalyst may be used.
No. The above reaction is carried out at 20 to 200 ° C., preferably 50 to 200 ° C.
It is preferable to carry out at a temperature of 150 ° C. for several hours. (C) water
Tri-terminal at the end of polyoxyalkylene polymer having acid group
Polyisocyanate compounds such as diisocyanate
To give an isocyanate group end,
The W group of the silicon compound represented by the formula (5) is
How to react. R¹ _3-a-SiX_a -R^Two W ... (5) (in the formula (5), R¹ , R^Two , X and a are the same as above. W is
Hydroxyl, carboxyl, mercapto and amino groups
An active hydrogen-containing group selected from (primary or secondary). (D) Powder of polyoxyalkylene polymer having hydroxyl group
After introducing an olefin group at the end, the olefin group,
A silicon compound represented by the formula (5) wherein W is a mercapto group:
Of reacting a mercapto group of a product. W is a mercapto group
As the silicon compound represented by the formula (5),
Mercaptopropyltrimethoxysilane, 3-mercap
Topropylmethyldimethoxysilane, 3-mercaptop
Propyl dimethylmethoxysilane, 3-mercaptopropi
Lutriethoxysilane, and the like. Of the above reaction
In this case, a polymerization initiator such as a radical generator may be used.
In some cases, radiation without using a polymerization initiator
Or by heat. As the polymerization initiator,
For example, peroxide-based, azo-based, or redox-based
And a metal compound catalyst. polymerization
Specific examples of the initiator include 2,2'-azobisisobu.
Thyronitrile, 2,2'-azobis-2-methylbutyro
Nitrile, benzoyl peroxide, t-alkyl peroxide
Oxyester, acetyl peroxide, diisopropyl
Luperoxy carbonate and the like. Also above
The reaction is carried out at a temperature of 20 to 200 ° C, preferably 50 to 150 ° C.
It is preferable to carry out for a period of time to several tens of hours. (When the main chain is other than polyoxyalkylene polymer)
The main chain of the polymer (A) is polyester or polycarbonate
In the case of the
Polyoxyalkanol is used as the starting polycarbonate
It can be produced by the same production method as that for the kilen polymer (C). Backbone
In the case of polyolefin, polybutadiene polyol or water
Hydroxyl-terminated polyoleate such as polybutadiene polyol
Polyoxyalkylene polymer (C) using fin as raw material
It can be manufactured by the same manufacturing method. In addition, 1,4-bis (1-
Chloro-1-methylethyl) benzene as initiator and trisalt
Depolymerization of isobutylene using boron chloride as catalyst
An isopropenyl group at the end, produced by a hydride reaction
From isobutylene-based polymer having
It can be produced by the same production method as the alkylene polymer (C). (Hydrolysable silicon group in which a in Formula (1) is 3)
A part of or all of the polymer (A) in the present invention is represented by the formula (1)
In which a is a hydrolyzable silicon group having 3 (hereinafter referred to as “hydrolyzable silicon group”).
Decomposable silicon group (H) ")
I need to do that. As "hydrolysable silicon group (H)"
X is an alkoxy group having 4 or less carbon atoms in the formula (1)
Having an alkoxy group having 4 or less carbon atoms
Trialkoxysilyl groups are particularly preferred. Trial Koki
Polymers with silyl groups are very reactive, especially
Very fast initial cure speed. Usually represented by equation (1)
In the hydrolysis reaction of the hydrolyzable silicon group
Generates silanol groups by reaction with water (-SiX
+ H_Two From silanol group represented by O → -SiOH + HX
Reaction), the resulting silanol groups condense,
Or a silanol group and a hydrolyzable silicon group
It is thought to proceed by a reaction that generates a xanthic bond (condensation reaction).
Has been obtained. Once silanol groups are generated,
It is considered that the condensation reaction proceeds smoothly. Trialkoxy
Ryl is an alkyldialkoxysilyl or dial
Silanol group generation compared to the alkyl alkoxysilyl group
The reaction rate is very fast at the beginning of the reaction. Accordingly
Thus, the curable composition of the present invention has sufficient strength properties in a short time.
And the time to reach adhesiveness is short.
It is considered to have an effect. Also trialkoxysil
Tri groups having an alkoxy group having a small carbon number
Alkoxysilyl groups have higher carbon numbers
Silanol group rather than trialkoxysilyl group
It is preferable because the reaction rate in the early stage of the generation reaction is high,
Trimethoxysilyl and triethoxysilyl groups are more preferred.
Preferably, the trimethoxysilyl group generates silanol groups.
Most preferred because the reaction speed is very fast in the early stages of
No. Therefore, as "hydrolyzable silicon group (H)"
Is most preferably a trimethoxysilyl group. Ma
And a hydrolyzable compound represented by the formula (1) in the polymer (A).
Ratio of hydrolyzable silicon group (H) in silicon group
Can vary depending on the application, required characteristics, and the like. polymerization
Isomer (A) is a hydrolyzable silicon group as the hydrolyzable silicon group.
When the polymer has only the i-group (H),
That is, the hydrolysis represented by the formula (1) in the polymer (A)
Almost 100% of the crystalline silicon groups (ie 80-100%)
Is a hydrolyzable silicon group (H), the curing rate
Has the effect of increasing the curability, which leads to the development of adhesion.
Particularly excellent room temperature curable compositions are obtained. In this case, the expression
90-1 of the hydrolyzable silicon group (H) represented by (1)
Of the hydrolyzable silicon group
(H) is preferable. Also, a in the formula (1) is
A hydrolyzable silicon group which is 1 or 2
When the base (H) is mixed, good elongation characteristics and
A room-temperature-curable composition that is compatible with fast-curing properties is obtained. This
In the case of the formula (1), all of the polymer (A) represented by the formula (1)
% Of hydrolyzable silicon group (H) in hydrolyzable silicon group
Preferably, the sum is 5 to 80%. Any percentage
Can be controlled freely according to the requirements
You. That is, the ratio of the hydrolyzable silicon group (H) is 5 to 5
At 0%, it improves curability and sealant
Can provide good elongation properties and flexibility required for
You. The ratio of the hydrolyzable silicon group (H) is 50 to 80.
%, The elongation characteristics required for elastic adhesives etc.
It is possible to sufficiently secure and dramatically improve the curability. Ma
In the hydrolyzable silicon group represented by the formula (1),
Hydrolyzable silicon groups other than the hydrolyzable silicon group (H)
A in the formula (1) is a hydrolyzable silicon group of 2
Particularly preferred. Di-containing alkoxy groups having 4 or less carbon atoms
Particularly preferred is an alkoxyalkylsilyl group.
No. A dimethoxymethylsilyl group is most preferred. formula
(1) a is a hydrolyzable silicon group in which a is 1 or 2,
Polymer (A) mixed with hydrolyzable silicon groups (H)
For example, the following methods (e) and (f)
Yes, the methods (e) and (f) may be used in combination. (E) As polymer (A), a in formula (1) is 1 or
A hydrolyzable silicon group and a hydrolyzable silicon group
A polymer having (H) is used. (F) As polymer (A), a in formula (1) is 1 or
Polyoxyalkyl having a hydrolyzable silicon group which is 2
Having a styrene polymer (C) and a hydrolyzable silicon group (H)
Both polymers (A) are used. Heavy in the present invention
The molecular weight of the union (A) depends on the intended use.
Although an appropriate value can be selected, the molecular weight of the polymer (A) is 800
It is preferably from 0 to 50,000. Flexibility is important
For applications such as sealants, the molecular weight is 8,000 to 50
000 polymers are preferred. The molecular weight is between 8000 and 25
000 is particularly preferable, 12000 to 200
Most preferably it is 00. In addition, strength is required
For applications such as adhesives, a molecular weight of 8,000 to 30,000
Polymers are preferred. If it is lower than 8000, the cured product is brittle.
If it is more than 30,000, it will be made because of high viscosity.
The workability deteriorates remarkably. The molecular weight is 8000-20,000
Is more preferably 12000 to 20000
It is particularly preferred that there is. (Polymerizable unsaturated group-containing monomer
(Polymer (E) Obtained by Polymerizing (D)) The room-temperature curable composition containing the polymer (A) as an essential component is hard.
Excellent in chemical properties. In the present invention, the polymer (A)
When using polyoxyalkylene polymer (C)
Means that the polyoxyalkylene polymer (C) is further polymerized
Obtained by polymerizing a monomer (D) containing a functional unsaturated group
It is preferable to contain (E). Contains polymer (E)
By doing so, adhesion at the initial stage of the curing reaction
Effect, that is, the time until the adhesive strength appears
An extremely short effect can be obtained. Contains polymerizable unsaturated group
Representative examples of the monomer (D) include, for example,
Compounds represented by (6) include, but are not limited to:
Not done. CRR^Five = CR^Three R^Four ... (6) (where R, R^Three , R^Four , R^Five Are each independently hydrogen
An atom, a halogen atom or a monovalent organic group. ) R, R^Five Wherein the organic group is monovalent having 1 to 10 carbon atoms
Is preferably a substituted or unsubstituted hydrocarbon group
No. R, R^Five Each is more preferably a hydrogen atom
New R^Three , R^Four Is an organic group having 1 to 10 carbon atoms.
Substituted or unsubstituted hydrocarbon group, alkoxy group,
Ruboxyl group, alkoxycarbonyl group, cyano group,
Ano group-containing group, alkenyl group, acyloxy group, carba
Moyl, pyridyl, glycidyloxy or gly
It is preferably a sidyloxycarbonyl group. R^Three 
Is a hydrogen atom, a halogen atom or a monovalent having 1 to 10 carbon atoms
Particularly preferred is a substituted or unsubstituted hydrocarbon group of
New Specific examples of the polymerizable unsaturated group-containing monomer (D)
Is styrene, α-methylstyrene, chlorostyrene
Any styrene monomer; acrylic acid, methacrylic acid,
Methyl acrylate, methyl methacrylate, ethyl acrylate
, Ethyl methacrylate, butyl acrylate, methacrylate
Butyl acrylate, 2-ethylhexyl acrylate, methacrylate
2-ethylhexyl luate, benzyl acrylate, methacrylate
Acrylic acid such as benzyl acrylate, methacrylic acid or
Ester, acrylamide, methacrylamide, etc.
Acrylic monomer of acrylonitrile, 2,4-disi
Cyano group-containing monomers such as anunobutene-1; vinyl acetate
And vinyl ester such as vinyl propionate
Body; die such as butadiene, isoprene, chloroprene
Monomer: vinyl glycidyl ether, allyl glycid
Jill ether, methallyl glycidyl ether, glycidyl
Acrylates and glycidyl methacrylates
Sidyl group-containing monomers; and other olefins,
Unsaturated esters, halogenated olefins, vinyl acetate
Tell and the like. Polymerizable unsaturated group-containing monomer
(D) may be used alone or in combination of two or more.
Is also good. Cyano group-containing monomer, glycidyl group-containing monomer
Or when styrene monomer is used, especially acrylonitrile
Tolyl, glycidyl acrylate, glycidyl methacrylate
Even better when using styrene or styrene
It is preferable because it can exhibit adhesiveness and mechanical properties. Also,
If rubber elasticity is required after curing,
It is preferable to use tellurium. Polymerizable unsaturated group-containing monomer
(D) a hydrolyzable silicon group represented by the formula (1)
Can be used. Such hydrolysis
Particularly preferred as the polymerizable monomer having a functional silicon group is the following formula
The compound represented by (7) is preferred. R⁷ -SiY_b R⁶ _3-b... (7) (in the formula (7), R⁷ Is a monovalent group having a polymerizable unsaturated group.
Machine, R⁶ Is substituted or unsubstituted having 1 to 20 carbon atoms
Y is a hydroxyl group or a hydrolyzable group
And b is 1, 2 or 3. Where R⁶ But
When several exist, their R⁶ Are the same or different
Often, when there are a plurality of Y,
May be different. ) As a polymerizable monomer having a hydrolyzable silicon group,
Vinyl monomer having water-decomposable silicon group,
An acrylic monomer having an i-group is exemplified. Concrete
Specifically, the following may be mentioned, and 3-acryloyloxy
Propyltrimethoxysilane, 3-methacryloyloxy
Cypropyltrimethoxysilane is particularly preferred. vinyl
Methyldimethoxysilane, vinylmethyldiethoxysila
, Vinylmethyldichlorosilane, vinyltrimethoxy
Silane, vinyltriethoxysilane, vinyltrichloro
Silane, tris (2-methoxyethoxy) vinylsilane
Vinylsilanes such as 3-acryloyloxypropyl
Methyldimethoxysilane, 3-methacryloyloxyp
Ropylmethyldimethoxysilane, 3-acryloyloxy
Cypropyl trimethoxysilane, 3-acryloyl oxy
Cypropyltriethoxysilane, 3-methacryloyl
Xypropyltrimethoxysilane, 3-methacryloyl
Acryloylamine such as oxypropyltriethoxysilane
Xysilanes, methacryloyloxysilanes and the like. this
In addition to these, for example, a polymer having 2 to 30 silicon atoms
A siloxane compound comprising a carbon-carbon double bond and
Compounds having a silicon atom combined with a hydrolyzable group
Can be used as a polymerizable monomer having a hydrolyzable silicon group
Wear. Polymerizable monomer having a hydrolyzable silicon group as described above
May be used alone or in combination of two or more.
No. Use a polymerizable monomer having a hydrolyzable silicon group
In this case, this monomer is a polymerizable unsaturated group-containing monomer (D) 1
It is preferable to use 0.01 to 20 parts by weight in 00 parts by weight.
No. Part or all of the polymerizable unsaturated group-containing monomer (D)
Has a polymerizable unsaturated group, and a glycidyl group and
And / or having a hydrolyzable silicon group represented by the formula (1)
It is preferably a monomer. (Polymer composition) Polyoxyalkylene polymer (C)
Has a polymer (E),
Polymer comprising a alkylene polymer (C) and a polymer (E)
The composition can be manufactured by the following methods (g) to (g).
You. (G) the polyoxyalkylene polymer (C) and
A polymer obtained by polymerizing the polymerizable unsaturated group-containing monomer (D)
A method of mixing the coalescence (E). (H) heavy in the polyoxyalkylene polymer (C)
A method of polymerizing a monomer (D) containing a compatible unsaturated group. (I) Polyoxyalkylene polymers containing unsaturated groups
The weight of the polymerizable unsaturated group-containing monomer (D) in (K)
After the polymerization, the remaining unsaturated group in the polymer (K) is
A method of converting into a hydrolyzable silicon group represented by (1).
The conversion method is based on hydrosilyl represented by the formula (3)
A method of reacting a compound is preferred. (N) In the precursor of the polyoxyalkylene polymer (C)
The polymerization of the polymerizable unsaturated group-containing monomer (D) was performed in
Later, the precursor is converted to a polyoxyalkylene polymer (C)
how to. (R) Contains polymerizable unsaturated groups in the presence of solvent or diluent
After polymerization of monomer (D), polyoxyalkylene
Mix with the polymer (C) and then add a solvent or
A method in which the diluent is distilled off. The solvent is a polymerizable unsaturated group-containing unit.
It can be appropriately selected according to the type of the monomer (D). As diluent
The unsaturated group-containing polyoxyalkylene polymer (K)
preferable. During the polymerization, the unsaturated groups in the solvent or diluent
Containing polyoxyalkylene polymer (K)
You can also. Polymerization of polymerizable unsaturated group-containing monomer (D)
In the case of using a polymerization initiator such as a radical generator
Often radiated without the use of polymerization initiators
It may be polymerized by wire or heat. Polymerization initiator, polymerization temperature
The degree and the polymerization time are the same as described in (d) above.
The same is true. When the polymer (E) is used in the present invention
Is a polyoxyalkylene polymer (C) / polymerized in a weight ratio.
Used within the range where the body (E) is 100/1 to 1/300
Preferably. 100/1 to 1/100, and more
Workability is used in the range of 100/1 to 1/10
It is particularly preferable in such points. The polymer (E) is a polyoxy
In the alkylene polymer (C), it is uniformly dispersed in fine particles.
Or it may be uniformly dissolved. Composition viscosity
When considering workability and workability, disperse them evenly into fine particles.
Is preferred. Epoxy resin used in the present invention
As (B), a commonly used epoxy resin is used.
Those which can be used and have two or more epoxy groups are particularly preferred.
New As a specific epoxy resin (B),
Nord A type epoxy resin, bisphenol F type epoxy
Resin, bisphenol S type epoxy resin, phenol
Volak epoxy resin, cresol novolak epoxy
Epoxy resin, bisphenol A novolak type epoxy resin
Fat, bisphenol F novolak epoxy resin, alicyclic
Formula epoxy resin, glycidyl ester type epoxy resin,
Glycidylamine type epoxy resin, hydantoin type epoxy
Epoxy resin, isocyanurate epoxy resin, resorci
Epoxy resins and their halides, hydrogen
Examples include, but are not limited to, additives. Book
In the invention, the proportion of the epoxy resin (B) used is determined by the polymer
When the polymer (E) is used in combination with (A),
The following range with respect to the sum of the polymer (A) and the polymer (E)
It is preferred that That is, (Polymer (A) or
Is the sum of the polymer (A) and the polymer (E)) / epoxy resin
(B) is 100/1 to 100/300 in weight ratio.
Is preferred. 1/100 to 100/1
Particularly preferred. Less epoxy resin (B)
In this case, the strength of the cured product becomes insufficient and
If not, the elongation will be insufficient. The composition of the present invention further comprises
May contain an epoxy curing agent (F).
Is preferred. As epoxy curing agent (F)
Generally used as a compound to cure epoxy resin (B)
What is used can be illustrated. Concrete epoxy hard
As the agent (F), diethylene triamine, triethylene
Aliphatic polyamines such as lenttetramine, m-phenylene
Aromatic polyamines such as diamines, secondary amines,
2,4,6-tris (dimethylaminomethyl) phenol
Tertiary amines such as toluene, salts thereof, acid anhydrides,
Polyamide resin, polysulfide resin, boron trifluoride
Complex compounds, imidazoles, dicyandiamides, etc.
Is mentioned. Also reacts with water to produce amines
Compounds can also be used as epoxy curing agents. For example, Dieci
Polyamines such as rentriamine and methyl ethyl ketone
Ketimine Compounds Obtained by the Dehydration of Carbonyl Compounds
Compounds, etc., which are known as
Not limited. When using epoxy curing agent (F)
The proportion used is the sum of the polymer (A) and the epoxy resin (B)
When the polymer (E) is used in combination, the polymer
(A), epoxy resin (B) and polymer (E)
Then, the following range is preferable. That is,
(Total or weight of polymer (A) and epoxy resin (B)
Combination of the union (A), the polymer (E) and the epoxy resin (B)
(Total) / (epoxy curing agent (F)) is 100 /
It is preferably 0.1 to 100/30. Of the present invention
The composition may further react with epoxy groups or epoxy groups
Contains a functional group and a hydrolyzable silicon group in the same molecule
Compound (G) may be contained. In the compound
Functional groups that can react with epoxy groups include amino groups,
A ruboxyl group, a mercapto group, and the like.
It is not limited to these. As the hydrolyzable silicon group,
The same group as the hydrolyzable silicon group contained in the polymer (A)
Is preferable, and a group represented by the formula (1) is preferable. Compound
(G) includes epoxy group-containing silanes and amino group-containing silanes.
Silanes, silanes containing mercapto groups, and carbohydrates
There are xyl group-containing silanes. Epoxy group-containing silanes
Specifically, 3-glycidoxypropyl trimeth
Xysilane, 3-glycidoxypropylmethyldimethoxy
Sisilane, 3-glycidoxypropyltriethoxysila
, 3- (N, N-diglycidyl) aminopropyltri
Methoxysilane, N-glycidyl-N, N-bis [3-
(Methyldimethoxysilyl) propyl] amine, N-g
Risidyl-N, N-bis [3- (trimethoxysilyl)
Propyl] amine and the like. Amino group-containing silanes
Specifically, 3-aminopropyltrimethoxysila
3-aminopropyltriethoxysilane, 3-amino
Nopropylmethyldimethoxysilane, N- (2-amino
Ethyl) -3-aminopropylmethyldimethoxysila
, N- (2-aminoethyl) -3-aminopropyl
Limethoxysilane, N, N-bis [3- (methyldimethoate
Xyloxy) propyl] amine, N, N-bis [3-
(Methyldimethoxysilyl) propyl] ethylene diamine
, N, N-bis [3- (trimethoxysilyl) propyl
Ru] ethylenediamine, N-[(3-trimethoxysilyl
Ru) propyl] diethylenetriamine [H_Two N (C_Two H
_Four NH)_Two C_Three H₆ Si (OCH_Three )_Three ], N-[(3
-Trimethoxysilyl) propyl] triethylenetetra
Min [H_Two N (C_Two H_Four NH)_Three C_Three H₆ Si (OCH
_Three )_Three ], 3-ureidopropyltriethoxysilane,
3-anilinopropyltrimethoxysilane and the like. Me
Specific examples of lecapto group-containing silanes include 3-mer
Captopropyltrimethoxysilane, 3-mercaptop
Ropirtriethoxysilane, 3-mercaptopropylmeth
Tyldimethoxysilane, 3-mercaptopropylmethyl
And diethoxysilane. Carboxyl group-containing silane
Specific examples include 2-carboxyethyltriet
Xysilane, 2-carboxyethylphenylbis (2-
Methoxyethoxy) silane, N- (N-carboxymethyl)
2-aminoethyl) -3-aminopropyltrimethoate
Xysilane and the like. When using compound (G)
The usage rate is the sum of the polymer (A) and the epoxy resin (B).
On the other hand, when the polymer (E) is used in combination, the polymer (A)
To the total of the epoxy resin (B) and the polymer (E)
The range is preferably as follows. That is, (polymerization
Total or polymer of body (A) and epoxy resin (B)
(Total of (A), polymer (E) and epoxy resin (B))
/ Compound (G) is 100 / 0.1 to 100/3 by weight
It is preferably 0. In the present invention, the composition
Hydrolyzable silicon group in the compound (A) or the compound (G)
A curing acceleration catalyst for accelerating the curing reaction may be used.
Alkyl titanate esters,
Silicon titanate, tin 2-ethylhexanoate and
Carboxylic acid metals such as dibutyltin dilaurate
Salts: dialkyltin oxide and bis (2-ethyl phthalate)
Esters such as lehexyl) and tetraethyl silicate
Reaction product with compound, dibutylamine-2-ethylhexa
Amine salts such as noate; aluminum tris (d)
Tyl acetoacetate), dialkyltin bisacetyl
Metal chelate compounds such as acetonate, and these
Metal salts, etc. and organic amine compounds, other acidic catalysts and bases
A neutral catalyst may be used. (Room temperature curable composition) The room temperature curable composition of the present invention is required.
But not fillers, plasticizers, curing accelerators, solvents,
Dehydrating agents, thixotropic agents, antioxidants, and other additives
Can also be included. Below, about those additives
explain. (Filler) As the filler, a known filler can be used.
The amount of filler used is polymer (A) or polymer (A).
0.001 to 1 based on a total of 100 parts by weight of the combined (E)
000 parts by weight, particularly preferably 50 to 250 parts by weight. Filling
The following are specific examples of the filler. these
May be used alone or in combination of two or more.
No. Surface treated with fatty acid or resin acid organic
Calcium carbonate, further pulverizing the calcium carbonate
Colloidal calcium carbonate with an average particle size of 1 μm or less
Light calcium carbonate having an average particle size of 1 to 3 μm
Charcoal such as heavy calcium carbonate having an average particle size of 1 to 20 μm
Calcium acid, fumed silica, precipitated silica, anhydrous
Silicic acid, hydrous silicic acid and carbon black, mug carbonate
Nesium, diatomaceous earth, calcined clay, clay, talc,
Titanium oxide, bentonite, organic bentonite, oxidized
Ferrous iron, zinc oxide, activated zinc flower, shirasu balloon, glass
Balloon, wood flour, pulp, cotton chips, mica, walnut
Flour, fir flour, graphite, aluminum fine powder,
Powder filler such as flint powder. Asbestos, glass fiber, moth
Lath filament, carbon fiber, Kevlar fiber, polyethylene
Fibrous filler such as ren fiber. (Plasticizer) As the plasticizer, a known plasticizer can be used.
The amount of the plasticizer used is the polymer (A) or the weight of the polymer (A).
0.001 to 1 based on a total of 100 parts by weight of the combined (E)
000 parts by weight are preferred. Specific examples of plasticizers are as follows
One. Dioctyl phthalate, diphthalic phthalate
Phthalates such as butyl and butylbenzyl phthalate
Kind. Dioctyl adipate, bis (2-methyl succinate)
Nonyl), dibutyl sebacate, butyl oleate, etc.
Aliphatic carboxylic esters. Pentaerythritol S
Alcohol esters such as ter. Trioctyl phosphate
And phosphate esters such as tricresyl phosphate. Epoki
Cyculated soybean oil, 4,5-epoxyhexahydrophthalic acid di
Epoxy such as octyl and epoxy benzyl stearate
Plasticizer. Chlorinated paraffin. Dibasic acid and dihydric alcohol
And polyesters such as polyesters
Plasticizer. Polyoxypropylene glycol and its derivatives
Polyethers, poly-α-methylstyrene,
Styrene oligomers such as polystyrene, polybutadi
Ene, butadiene-acrylonitrile copolymer, polyc
Loloprene, polyisoprene, polybutene, hydrogenated polybu
And oligomers such as epoxidized polybutadiene
Polymer plasticizer. (Curing Acceleration Catalyst) The curable composition of the present invention is cured.
Accelerates the curing reaction of silicon groups containing hydrolyzable groups
A curing accelerator catalyst may be used. As a specific example
Include the following compounds. One or two of them
The above is used. The curing accelerating catalyst is polymer (A) or
For a total of 100 parts by weight of the polymer (A) and the polymer (E)
It is preferable to use 0.0001 to 10 parts by weight.
Alkyl titanate, organosilicon titanate, bismuth
Metal salts such as tris (2-ethylhexanoate), phosphorus
Acidic compounds such as acid, p-toluenesulfonic acid, phthalic acid, etc.
Substance, butylamine, hexylamine, octylamine,
Aliphatic monoamines such as decylamine and dodecylamine,
Aliphatic such as ethylenediamine and hexamethylenediamine
Diamine, diethylenetriamine, triethylenetetra
Aliphatic polyamines such as amine and tetraethylenepentamine
, Heterocyclic amines such as piperidine and piperazine, m
-Aromatic amines such as phenylenediamine, ethanol
Amines, triethylamine, epoxy resin curing agent
Compounds, such as various modified amines, used as a catalyst. 2-
Tin ethylhexanoate, tin naphthenate, stearic acid
A mixture of a divalent tin compound such as tin and the above amines. The
Butyltin diacetate, dibutyltin dilaurate,
Dioctyltin dilaurate and the following carboxylic acid types
Organotin compounds and their carboxylic acid-type organotins
A mixture of the compound and the above amines. (n-C_FourH₉)_TwoSn (OCOCH =
CHCOOCH_Three)_Two, (N-C_FourH₉)_TwoSn (OCOCH = CHCOOC_FourH₉-n)_Two , (N-C
₈H₁₇)_TwoSn (OCOCH = CHCOOCH_Three)_Two , (N-C₈H₁₇)_TwoSn (OCOCH = CHC
OOC_FourH₉-n)_Two, (N-C₈H₁₇)_TwoSn (OCOCH = CHCOOC₈H₁₇-iso)_Two .
The following sulfur-containing organotin compounds. (n-C_FourH₉)_TwoSn (SCH_TwoCO
O), (n-C₈H₁₇)_TwoSn (SCH_TwoCOO), (n-C₈H₁₇)_TwoSn (SCH_TwoCH_TwoCO
O), (n-C₈H₁₇)_TwoSn (SCH_TwoCOOCH_TwoCH_TwoOCOCH_TwoS), (n-C_FourH₉)_TwoS
n (SCH_TwoCOOC₈H₁₇-iso)_Two, (N-C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇-is
o)_Two , (N-C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇-n)_Two , (N-C_FourH₉)_TwoSn
S. (n-C_FourH₉)_TwoSnO, (n-C₈H₁₇)_TwoOrganic tinoxy such as SnO
And their organotin oxides and ester compounds
Reaction product with Ethyl silique as an ester compound
Salt, dimethyl maleate, diethyl maleate, male
Dioctyl citrate, dimethyl phthalate, diethyl phthalate
And dioctyl phthalate. Sharpness such as the following
Tin compounds and their tin compounds and alkoxy
Reaction product with silane (acac is acetyl
Represents the setnato ligand). (n-C_FourH₉)_TwoSn (acac)_Two, (N-C₈H
₁₇)_TwoSn (acac)_Two , (N-C_FourH₉)_Two (C₈H₁₇O) Sn (acac). below
Tin compounds. (n-C_FourH₉)_Two(CH_ThreeCOO) SnOSn (OCOCH_Three) (C_FourH₉-n)
_Two , (N-C_FourH₉)_Two(CH_ThreeO) SnOSn (OCH_Three) (C_FourH₉-n)_Two . (Solvent) The composition of the present invention is used as a curable composition.
In order to adjust the viscosity and improve the storage stability of the composition,
Then, a solvent can be added. Solvent usage is heavy
Combined (A) or a total of 1 of polymer (A) and polymer (E)
0.001 to 500 parts by weight is preferable for 00 parts by weight
No. Solvents include aliphatic hydrocarbons and aromatic hydrocarbons
, Halogenated hydrocarbons, alcohols, ketones,
Esters, ethers, ester alcohols, keto
Alcohols, ether alcohols, ketone ethers
, Ketone esters and ester ethers
Wear. Alcohols preserve the compositions of the present invention for long periods of time.
Is preferable because storage stability is improved. Alcow
The alkyls include alkyl alcohols having 1 to 10 carbon atoms.
Preferably, methanol, ethanol, isopropanol
, Isopentyl alcohol, hexyl alcohol, etc.
Particularly preferred. (Dehydrating agent) Further, the storage stability of the curable composition of the present invention is improved.
Further improve curability and flexibility.
A small amount of a dehydrating agent can be added within a range not present. Dehydrating agent usage
Is the polymer (A) or the total of the polymer (A) and the polymer (E).
0.001 to 30 parts by weight is preferable for 100 parts by weight in total.
New Specifically, methyl orthoformate, ethyl orthoformate
Alkyl orthoformate such as methyl, methyl orthoacetate, ortho
Alkyl orthoacetate such as ethyl acetate, methyltrimethoxy
Sisilane, vinyltrimethoxysilane, tetramethoxy
Hydrolyzable organic silicon such as silane and tetraethoxysilane
Use compound, hydrolyzable organic titanium compound, etc.
You. Vinyltrimethoxysilane, tetraethoxysilane
Is particularly preferred in terms of cost and effect. (Thixotropic agent) Also with thixotropic properties to improve sagging
An additive may be used. As such a thixotropic agent,
For example, hydrogenated castor oil, fatty acid amide and the like are used. (Anti-aging agent) Also, as an anti-aging agent, generally used
Antioxidants, UV absorbers, and light stabilizers
Used. Hindered amine, benzotriazole
System, benzophenone system, benzoate system, cyanoacryl
Rate type, acrylate type, hindered phenol type,
Phosphorus-based and sulfur-based compounds can be used as appropriate. (Others) In addition, paint adhesion and surface tack over a long period
Air-curable compounds and photo-curable
Compounds can be added. The amount of air oxidation curable compound used is heavy
Combined (A) or a total of 1 of polymer (A) and polymer (E)
0.001 to 50 parts by weight with respect to 00 parts by weight, photocurable
The amount of the compound used is polymer (A) or polymer (A).
0.001 to 5 with respect to a total of 100 parts by weight of the combined (E)
0 parts by weight is preferred. Such an air oxidation curable compound
Oils such as tung oil, linseed oil, etc.
Various alkyd resins and drying oils obtained by modifying the compound
More modified acrylic polymer, silicone resin,
Libutadiene, a polymer or copolymer of diene having 5 to 8 carbon atoms
Diene-based polymers such as polymers, and the polymers and copolymers
Modified products (maleated, boiled oil, etc.)
Is mentioned. Photo-curable compounds include polyfunctional acrylics.
Rates are commonly used. Other pigments include iron oxide,
Inorganic pigments such as chromium oxide and titanium oxide, and phthalocyanine
Organic pigments such as nin blue and phthalocyanine green
No. The room temperature-curable composition of the present invention comprises
For waterproofing, waterproofing, adhesives, coatings, etc.
In particular, sufficient cohesion of the cured product itself and dynamic followability to adherends
It is suitable for the use where is required.

EXAMPLES The polymers (P1 to P1) produced in Production Examples 1 to 20 were prepared.
Examples and comparative examples in which a cured product was produced using the method described in 20) are shown below. In addition, a part shows a weight part. Production Example 1
In 10, the term "hydroxyl equivalent molecular weight" refers to the molecular weight calculated from the hydroxyl value of a polyoxyalkylene polymer having a hydroxyl group as a raw material. M _w / M _n is a value measured by gel permeation chromatography using tetrahydrofuran as a solvent. A calibration curve was created using a polyoxyalkylene polyol. Production Examples 11 to 12
In, the molecular weight was measured by gel permeation chromatography using tetrahydrofuran as a solvent. The calibration curve was created using polystyrene. (Production Example 1) Propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Hydroxyl value converted molecular weight 17000,
In addition, a methanol solution of sodium methoxide was added to polypropylene oxide having M _w / M _n = 1.3, and methanol was distilled off under reduced pressure under heating to convert the terminal hydroxyl group of polypropylene oxide into sodium alkoxide. Next, allyl chloride was reacted. Removing unreacted allyl chloride,
Purification gave an allyl group-terminated polypropylene oxide (this is referred to as polymer U1). The polymer U1 was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P1 having a trimethoxysilyl group at a terminal. (Production Example 2) Polypropylene oxide having a hydroxyl value-converted molecular weight of 17000 and _Mw / _Mn = 1.3 obtained by reacting propylene oxide with propylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Was used to obtain a polypropylene oxide having an allyl group at the terminal in the same manner as in Production Example 1. The reaction product was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P2 having a terminal trimethoxysilyl group. (Production Example 3) A hydroxyl value-converted molecular weight of 170 obtained by reacting propylene oxide with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst.
A polypropylene oxide having an allyl group at the end was obtained in the same manner as in Production Example 1 using polypropylene oxide of 00 and _Mw / _Mn = 1.3. The reaction product was reacted with a mixture of methyldimethoxysilane, which is a hydrosilyl compound, and trimethoxysilane at a molar ratio of 30:70 in the presence of a platinum catalyst, and a methyldimethoxysilyl group and trimethoxysilyl were added to the terminals. A polymer P3 having both groups was obtained. (Production Example 4) A hydroxyl value-converted molecular weight of 170 obtained by reacting propylene oxide with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst.
A polypropylene oxide having an allyl group at the end was obtained in the same manner as in Production Example 1 using polypropylene oxide of 00 and _Mw / _Mn = 1.3. This reaction product is reacted with 3-mercaptopropyltrimethoxysilane as a silyl compound using 2,2′-azobis-2-methylbutyronitrile as a polymerization initiator, and a trimethoxysilyl group is added to a terminal. Having a polymer P4. (Production Example 5) Polymerization of propylene oxide was carried out using zinc hexacyanocobaltate catalyst with glycerin as an initiator to obtain a hydroxyl value-converted molecular weight of 17000 and M _w / M
After obtaining polyoxypropylene triol with _n = 1.3, purification was performed. Isocyanatepropyltrimethoxysilane was added thereto, and a urethanation reaction was performed to convert both ends into trimethoxysilyl groups, thereby obtaining a polymer P5 having a molecular weight of 18,000. (Production Example 6) Hydroxyl equivalent molecular weight 170 obtained by reacting propylene oxide with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst.
A polypropylene oxide having an allyl group at the end was obtained in the same manner as in Production Example 1 using polypropylene oxide of 00 and _Mw / _Mn = 1.3. This reaction product was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P6 having a methyldimethoxysilyl group at a terminal. (Production Example 7) Polypropylene oxide having a hydroxyl value-converted molecular weight of 7000 and M _w / M _n = 1.2 obtained by reacting propylene oxide with propylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst Was used to obtain a polypropylene oxide having an allyl group at the terminal in the same manner as in Production Example 1. This reaction product was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P7 having a methyldimethoxysilyl group at a terminal. (Production Example 8) Polypropylene oxide having a hydroxyl value-converted molecular weight of 7000 and _Mw / _Mn = 1.2 obtained by reacting propylene oxide with propylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst Was used to obtain a polypropylene oxide having an allyl group at the terminal in the same manner as in Production Example 1. The reaction product was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P8 having a terminal trimethoxysilyl group. (Production Example 9) A methanol solution of sodium methoxide was added to polyoxypropylene diol having a hydroxyl value-equivalent molecular weight of 3,000 obtained using a potassium hydroxide catalyst,
The methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group into sodium alkoxide. Next, the reaction product was reacted with chlorobromomethane to increase the molecular weight, and subsequently reacted with allyl chloride to obtain a polypropylene oxide having an allyloxy group at the terminal (M _w / M _n = 1.9). This was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P9 having a trimethoxysilyl group at a terminal and a molecular weight of 7000. (Production Example 10) A polyoxypropylene diol having a hydroxyl value-converted molecular weight of 6000 and a _Mw / _Mn = 1.9 obtained using a potassium hydroxide catalyst was used. A polyoxypropylene having a group was obtained. This was reacted with trimethoxysilane as a hydrosilyl compound in the presence of a platinum catalyst to obtain a polymer P10 having a terminal trimethoxysilyl group. (Production Example 11) Based on the method described in JP-A-1-170681, isobutylene was polymerized using 1,4-bis (1-chloro-1-methylethyl) benzene as an initiator and boron trichloride as a catalyst, followed by removal. An isobutylene polymer having a molecular weight of about 5000 and having isopropenyl groups at both ends at a ratio of about 92% produced by hydrogen chloride is reacted with trichlorosilane at 90 ° C. for 12 hours using chloroplatinic acid as a catalyst. By reacting methyl and methanol, a polyisobutylene-based polymer P11 having a trimethoxysilyl group at a terminal was obtained. (Production Example 12) Based on the method described in JP-A-1-170681, isobutylene was polymerized using 1,4-bis (1-chloro-1-methylethyl) benzene as an initiator and boron trichloride as a catalyst, followed by removal. Isobutylene polymer having a molecular weight of about 5000 and having isopropenyl groups at both ends at a ratio of about 92% produced by hydrogen chloride is reacted with methyldichlorosilane at 90 ° C. for 12 hours using chloroplatinic acid as a catalyst. By reacting methyl acid and methanol, a polyisobutylene-based polymer P12 having a methyldimethoxysilyl group at a terminal was obtained. (Production Example 13) 90 mol% of 3-isocyanatopropyltrimethoxysilane was reacted with the terminal hydroxyl group of a hydrogenated polybutadiene having a hydroxyl group at the terminal (Polytail HA, manufactured by Mitsubishi Chemical Corporation) to form a trimethoxysilyl group at the terminal A hydrogenated polybutadiene polymer P13 having the following formula: was obtained. (Production Example 14) 90 mol% of 3-isocyanatopropylmethyldimethoxysilane was reacted with the terminal hydroxyl group of hydrogenated polybutadiene having a hydroxyl group at the terminal (Polytail HA, manufactured by Mitsubishi Chemical Corporation) to give a methyldimethoxysilyl group at the terminal A hydrogenated polybutadiene polymer P14 having the following formula: was obtained. (Production Example 15) 50 g of 30 g of polymer P1 was 30
Placed in a 0 cm ³ four-necked flask. While maintaining the temperature at 110 ° C., a mixture of the remaining 20 g of the polymer P1, 15 g of styrene, 15 g of acrylonitrile and 0.6 g of azobisisobutyronitrile was added dropwise over 2 hours while stirring under a nitrogen atmosphere. Thereafter, stirring was continued at the same temperature for 0.5 hour. After completion of the reaction, the unreacted monomer
The polymer was removed by heating under reduced pressure and deaeration with Hg for 2 hours to obtain a polymer P15. (Production Example 16) Polymer P16 was produced in the same manner as in Production Example 15 except that polymer P6 (methyldimethoxysilyl group terminal) was used instead of polymer P1 (trimethoxysilyl group terminal) as a raw material. . (Production Example 17) 100 g of polymer P1 was placed in a reactor equipped with a stirrer, and diluted with 50 g of toluene. The mixture was heated to 100 ° C., and 20 g of acrylonitrile, 20 g of styrene, 5 g of glycidyl methacrylate and
-Methacryloyloxypropyltrimethoxysilane 2
A solution in which 0, 3 g of 2,2'-azobisisobutyronitrile was dissolved in g was added dropwise over 3 hours with stirring. After completion of the dropwise addition, 2,2'-azobisisobutyronitrile was added to the mixture at 0.1.
After dropping 2 g of toluene solution over 30 minutes, 100
The mixture was heated and stirred at ℃ for 3 hours. 100 ° C from the resulting mixture
The toluene was distilled off under reduced pressure to obtain a cloudy polymer P17. (Production Example 18) Polymer P18 was produced in the same manner as in Production Example 17, except that polymer P6 (methyldimethoxysilyl group terminal) was used instead of polymer P1 (trimethoxysilyl group terminal) as a raw material. . (Production Example 19) 100 g of the polymer P1 was placed in a reactor equipped with a stirrer. This is heated to 100 ° C., and styrene 5
g, methyl methacrylate 10 g, butyl methacrylate 7
g, 2 g of octadecyl methacrylate, 18 g of 3-methacryloyloxypropyltrimethoxysilane, 2,2 ′
A solution of 0 and 5 g of azobisisobutyronitrile was added dropwise with stirring over 3 hours. After completion of the dropwise addition, a toluene solution of 0.2 g of 2,2′-azobisisobutyronitrile was further added dropwise over 30 minutes, and the mixture was heated and stirred at 100 ° C. for 3 hours. From the obtained mixture, toluene was distilled off under reduced pressure at 100 ° C. to obtain a cloudy polymer P19. (Production Example 20) A polymer P20 was produced in the same manner as in Production Example 19, except that the raw material was a polymer P6 (methyldimethoxysilyl group terminal) instead of the polymer P1 (trimethoxysilyl group terminal). . (Examples 1 to 6 and Comparative Examples 1 to 5) Polymers P1 to P1
0, 100 parts of the polymer shown in Table 1 or Table 2, 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy), and 5 parts of 2,4,6-tris (dimethylaminomethyl) phenol , And 2 parts of dibutyltin dilaurate were added and mixed well to obtain a composition. In Example 4, only 100 parts of a mixture obtained by mixing P1 and P8 at a weight ratio of 7/3 was used as the polymer. (Example 7 and Comparative Example 6) Organic polymer P1 or P6
Among them, 100 parts of the polymer shown in Table 1 or 2, Epicoat 828 (bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd.)
(Type epoxy resin), 50 parts of 2,4,6-tris (dimethylaminomethyl) phenol, 2 parts of dibutyltin dilaurate, and 2 parts of 3-aminopropyltrimethoxysilane are added and mixed well to obtain a composition. Was. <Adhesion test> Length 100mm, width 20mm, thickness 1m
m, the coated surfaces of the two aluminum plates were wiped with a solvent, the above-described compositions were applied to the respective surfaces, and a test piece was formed using a spacer such that the composition layer had a length of 70 mm, a width of 20 mm, and a thickness of 1 mm. The T-peel strength (unit: kg / 25 mm) at each time point of production and curing at 20 ° C. for 1 day and 7 days, and further at 50 ° C. for 7 days, at a pulling speed of 200 mm / min according to JIS K 6854. It was measured. The results are shown in Tables 1 and 2. (Examples 8 to 10 and Comparative Examples 7 to 8) Polymer (P11
To P14), 100 parts of the polymer shown in Table 3, colloidal calcium carbonate (Shiraishi Kagaku Kogyo CCR) 50
Parts, Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), 50 parts, 2,4,6-tris (dimethylaminomethyl) phenol, 5 parts, and sodium sulfate hydrate, 5 parts, and hinder Dophenolic antioxidant (Irganox 2 manufactured by Ciba-Geigy)
45) 2 parts, 2 parts of a hindered amine light stabilizer (LA63, manufactured by Asahi Denka Kogyo KK), 1 part of 3- (N-2-aminoethyl) aminopropyltrimethoxysilane, 2 parts of 3-glycidyloxypropyltrimethoxysilane Mix well,
Finally, 2 parts of dibutyltin bisacetylacetonate were quickly mixed to obtain a composition. In Example 10, P11
A polymer mixed at / P12 = 1/1 (weight ratio) was used. Table 3 shows the results of the adhesion test performed in the same manner as in Example 1. (Examples 11 to 14 and Comparative Examples 9 to 11) Polymer (P
15 to P20), 100 parts of a polymer shown in Table 4, colloidal calcium carbonate (Shiraishi Kagaku Kogyo CCR)
50 parts, Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) 50 parts, 2, 4, 6
5 parts of tris (dimethylaminomethyl) phenol and 5 parts of sodium sulfate hydrate were added, and 2 parts of a hindered phenol-based antioxidant (Irganox 245 manufactured by Ciba Geigy) and a hindered amine-based light stabilizer (Asahi Denka Kogyo Co., Ltd.) LA63) 2 parts, 3-aminopropyltrimethoxysilane 1 part, 3-glycidoxypropyltrimethoxysilane 1 part are mixed well, and finally, dibutyltin bisacetylacetonate 2 parts is quickly mixed to form a composition. Obtained. In Example 14, a mixture of P15 / P16 = 1/1 (weight ratio) was used as a polymer. Table 4 shows the results of the adhesion test performed in the same manner as in Example 1.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

As described above, the room temperature curable composition of the present invention is excellent in curability, and particularly, the time required to develop adhesiveness is extremely short.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/10 C08L 101/10 F term (Reference) 4J002 AC033 AC063 AC093 BB013 BB20X BC033 BC093 BC113 BD013 BE043 BF013 BF023 BG013 BG043 BG053 BG063 BG093 BG103 BG133 CD02W CD05W CD06W CD08W CD11W CD12W CD13W CD14W CD193 CF03X CG02X CH05X CL014 CN024 EN046 EN076 ET006 EU116 EX037 EX067 EX077 EX087 EY016 FD010 FD020 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030 FD030

Claims (14)

[Claims] 1. A polymer having a hydrolyzable silicon group represented by the following formula (1), wherein a part or all of the polymer is a hydrolyzable silicon group of the formula (1) wherein a is 3. A room temperature curable composition comprising, as essential components, a polymer (A) which is a polymer having the formula (I) and an epoxy resin (B). -SiX _a R ¹ _3-a in (1) (Formula (1), R ¹ is a monovalent organic group, substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, a
Represents 1, 2 or 3. However, when a plurality of R ¹ are present, those R ¹ may be the same or different, and X 1
When there are a plurality of, Xs thereof may be the same or different. ) 2. The polymer (A) has a molecular weight of 8,000 to 500.
The room temperature curable composition according to claim 1, which is 00. 3. The room temperature curable composition according to claim 1, wherein the polymer (A) is a polyoxyalkylene polymer (C) having a hydrolyzable silicon group represented by the formula (1). . 4. The room-temperature curable composition according to claim 3, wherein the molecular weight distribution M _w / M _{n of the} polyoxyalkylene polymer (C) is 1.7 or less. 5. A polyoxyalkylene polymer (C) is obtained by polymerizing a cyclic ether with a double metal cyanide complex as a catalyst in the presence of an initiator at the end of a polyoxyalkylene polymer represented by the formula (1): 5. A polymer obtained by introducing a hydrolyzable silicon group represented by the formula:
The room temperature curable composition according to the above. 6. A polyoxyalkylene polymer (C) obtained by polymerizing a cyclic ether in the presence of an initiator and having a molecular weight distribution M _w / M _n of 1.7 or less. 4. A polymer obtained by introducing a hydrolyzable silicon group represented by the formula (1) into a terminal.
6. The room temperature curable composition according to 4 or 5. 7. The polyoxyalkylene polymer (C) further comprises a polymer (E) obtained by polymerizing a polymerizable unsaturated group-containing monomer (D). 7. The room temperature curable composition according to 5 or 6. 8. A polymer (E) obtained by further polymerizing a polymerizable unsaturated group-containing monomer (D) in the polyoxyalkylene polymer (C). The room temperature curable composition according to claim 3, 4, 5 or 6, comprising: 9. The polymerizable unsaturated group-containing monomer (D) has a polymerizable unsaturated group in part or all and has a glycidyl group and / or a hydrolysis represented by the formula (1). The room temperature curable composition according to claim 7, which is a monomer having a functional silicon group. 10. A part or all of the polymer (A) is a hydrolyzable silicon group wherein a in the formula (1) is 1 or 2 and a hydrolyzable silicon group wherein a in the formula (1) is 3 It is a polymer which has a silicon group together, Claims 1, 2, 3, 5, 6, 7,
10. The room temperature curable composition according to 8 or 9. 11. A polymer having a hydrolyzable silicon group wherein a in the formula (1) is 1 or 2, and a hydrolyzable silicon group wherein a in the formula (1) is 3 Claims 1, 2, 3, 5, 6, comprising both polymers having groups.
10. The room temperature curable composition according to 7, 8 or 9. 12. The polymer according to claim 1, wherein the polymer (A) has only a hydrolyzable silicon group in which a in the formula (1) is 3 as a hydrolyzable silicon group. 5, 6,
10. The room temperature curable composition according to 7, 8 or 9. 13. A method according to claim 1, further comprising an epoxy curing agent (F).
13. The room temperature curable composition according to 1 or 12. 14. A compound (G) containing an epoxy group or a functional group capable of reacting with an epoxy group and a hydrolyzable silicon group in the same molecule.
The room temperature curable composition according to 5, 6, 7, 8, 9, 10, 11, 12, or 13.