JPH1121463A - Room temperature-curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition improved in curability, capable of giving a cured product exhibiting tensile shear properties inherent therein in a short time, and useful as a sealant or adhesive, by including a polymer bearing specific hydrolyzable silicon group, a curing catalyst, and a specific silicon compound. SOLUTION: This composition is obtained by incorporating (A) 100 pts.wt. of a polymer bearing hydrolyzable silicon group of the formula SiXa R3-a (R is a 1-20C monovalent organic group; X is OH, etc.; (a) is 1, 2 or 3) (in the present case, (a)=3), with the main chain being pref. a polyoxyalkylene chain, with (B) 0.001-10 pts.wt. of a curing catalyst (e.g. an alkyl ester titanate salt) and (C) 0.01-20 pts.wt. of a low-molecular silicon compound bearing hydrolyzable silicon group of the formula SiX<1> b R<1> 3-b (R<1> is a 1-20C monovalent organic group; X<1> is OH, etc.; (b) is 1, 2 or 3) and functional group (e.g. hydroxyl group, mercapto group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a room temperature curable composition which cures in the presence of moisture.

[0002]

2. Description of the Related Art A method of curing various polymers having a hydrolyzable silicon group at a terminal and using them in sealants, adhesives and the like is well known and is an industrially useful method.
Among such polymers, particularly those having a main chain of polyoxyalkylene are liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and is used as a sealant, an adhesive or the like. It has preferable characteristics.

[0003] Such moisture-curable polymers include:
Polymers having a terminal hydrolyzable silicon group described in JP-A-3-72527, JP-A-3-47825 and the like can be mentioned. Such a polymer having a hydrolyzable silicon group at a terminal usually has a hydrolyzable silicon group in which two hydrolyzable groups are bonded to one silicon atom in order to maintain elongation and flexibility.

However, for each such silicon atom, 2
A polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups is inferior in curability, and in particular, has a poor internal curability under low-temperature conditions, so that a cured product exhibiting sufficient strength characteristics can be obtained in a short time. There was a problem that it was not possible.

[0005]

Therefore, the curing properties of a polymer having a hydrolyzable silicon group can be improved without greatly deteriorating its flexibility and workability, and the final strength can be improved even at a low temperature. Can greatly reduce the time to reach,
As a result of examining a composition that can exhibit the inherent tensile shear characteristic of the cured product in a short time, the present invention has been achieved.

[0006]

The present invention relates to a room-temperature curable composition containing a polymer having a hydrolyzable silicon group represented by the following general formula (1). a) a polymer having a hydrolyzable silicon group (A), a curing catalyst (B), and a silicon compound (C-
It is a room temperature curable composition containing the silicon compound (C) comprising 1) and / or (C-2).

-SiX _a R _3-a (1) (In the general formula (1), R is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and X is a hydroxyl group or a hydrolyzed group. Is a decomposable group, and a is 1, 2 or 3. However, when a plurality of Rs are present, they may be the same or different, and when a plurality of Xs exist, they may be the same or different.)

Silicon compound (C): (C-1): a low molecular weight silicon compound having a hydrolyzable silicon group and a functional group represented by the general formula (2). (C-2): a reaction product obtained by reacting two or more low-molecular silicon compounds (C-1) each having a functional group that can react with each other, among the low-molecular silicon compounds (C-1).

[0009] During ^{_{-SiX 1 b R 1 3-b}} ··· (2) ( the formula (2), R ¹ is a monovalent organic group, substituted or unsubstituted 1 to 20 carbon atoms, X ¹ Is a hydroxyl group or a hydrolyzable group, and b is 1, 2 or 3.
When a plurality of R ¹ are present, they may be the same or different,
When a plurality of X ¹ are present, they may be the same or different. )

The polymer used in the present invention has a hydrolyzable silicon group represented by the above general formula (1) at a molecular chain terminal or a side chain. Examples of the main chain of the polymer include a polyoxyalkylene chain, a polyester chain, a polycarbonate chain, and a polyolefin chain. Preferably, the backbone is essentially a polyoxyalkylene chain.

Such a polymer is disclosed in, for example,
47825, JP-A-3-72527, JP-A-3-796
27, JP-B-46-30711, JP-B-45-3631
9. Proposed in Japanese Patent Publication No. 46-17553.

The polymer having a main chain of polyoxyalkylene will be described below. Such a polymer is preferably produced by using a polyoxyalkylene compound having a functional group as a raw material as described below, and introducing a hydrolyzable silicon group into the terminal via an appropriate organic group.

The starting polyoxyalkylene compound is preferably a hydroxyl-terminated compound produced by reacting an initiator such as a hydroxy compound having one or more hydroxyl groups with a monoepoxide or the like in the presence of a catalyst.

The monoepoxide includes ethylene oxide, propylene oxide, butylene oxide, hexylene oxide and the like. Tetrahydrofuran and the like can also be used. Examples of the catalyst include an alkali metal catalyst such as a potassium compound and a cesium compound, a double metal cyanide complex catalyst, and a metal porphyrin catalyst.

When a high molecular weight polyoxyalkylene compound is used as the raw material polyoxyalkylene compound, a relatively low molecular weight polyoxyalkylene compound produced by an alkali catalyst or the like is reacted with a polyhalogen compound such as methylene chloride. Thus, a polyoxyalkylene compound obtained by multiplying can be used.

The polyoxyalkylene compound produced using the double metal cyanide complex catalyst has a narrower molecular weight distribution and better curability than that obtained when an alkali catalyst is used. preferable.

The complex metal cyanide complex is preferably a complex containing zinc hexacyanocobaltate as a main component.
Their ether and / or alcohol complexes are particularly preferred. Its composition can be essentially the one described in JP-B-46-27250. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable in terms of handling during the production of the complex. As the alcohol, JP-A-4-145123
Are preferred.

The number of functional groups of the starting polyoxyalkylene compound is preferably 2 or more, and 2 or 3 is particularly preferable when the flexibility of the cured product is to be emphasized, and 3 to 8 when the adhesion or curability is to be emphasized. Is particularly preferred.

Specific examples of the raw material polyoxyalkylene compound include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, and copolymers thereof.

Particularly preferred starting polyoxyalkylene compounds are polyoxypropylene diol and polyoxypropylene triol. When used in the following methods (a) and (d), olefin-terminated polyoxyalkylene compounds such as allyl-terminated polyoxypropylene monol can also be used.

The hydrolyzable silicon group represented by the general formula (1) will be described. In the general formula (1), R represents 1 to 2 carbon atoms.
0 substituted or unsubstituted monovalent organic group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, still more preferably an alkyl group having 8 or less carbon atoms, phenyl Or a fluoroalkyl group. Particularly preferred are a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group and the like. When a plurality of Rs are present, they may be the same or different.

Examples of the hydrolyzable group for X include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group,
And a hydride group.

Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, particularly preferably 4 or less. Desirable X is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group, a propoxy group or a propenyloxy group. When a plurality of Xs are present, they may be the same or different.

A is 1, 2 or 3. The number of hydrolyzable silicon groups in the polymer is preferably from 1 to 8, and particularly preferably from 2 to 6.

The method of introducing the hydrolyzable silicon group into the starting polyoxyalkylene compound is not particularly limited,
For example, the starting polyoxyalkylene compound can be appropriately introduced through an organic group by the following methods (a) to (d).

(A) A method of reacting a polyoxyalkylene compound having a hydroxyl group into which an olefin group is introduced at a terminal with a hydrosilyl compound represented by the general formula (3). HSiX _a R _3-a (3) (In the general formula (3), R, X and a are the same as described above.)

Here, as a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene compound, and the compound is bonded through an ether bond, an ester bond, a urethane bond or a carbonate bond. Or a method of introducing an olefin group into a side chain of a raw material polyoxyalkylene compound by adding and copolymerizing an olefin group-containing epoxy compound such as allyl glycidyl ether when polymerizing an alkylene oxide. .

(B) A method in which a compound represented by the general formula (4) is reacted with a terminal of a polyoxyalkylene compound having a hydroxyl group. R _3-a -SiX _a -R ² NCO (4) (In the general formula (4), R, X and a are the same as above. R ² is a divalent hydrocarbon group having 1 to 17 carbon atoms.) )

(C) A polyisocyanate compound such as tolylene diisocyanate is reacted with the terminal of a polyoxyalkylene compound having a hydroxyl group to form an isocyanate group terminal, and the silicon compound represented by the general formula (5) is added to the isocyanate group. Reacting the W group of R _3-a -SiX _a -R ² W (5) (In the general formula (5), R, R ² , X and a are the same as described above. W
Is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary). )

(D) An olefin group is introduced into the terminal of a polyoxyalkylene compound having a hydroxyl group, and the olefin group is reacted with a mercapto group of a silicon compound represented by the general formula (5) wherein W is a mercapto group. Method.

The composition of the present invention comprises a compound represented by the general formula (1)
It is necessary to contain a polymer having a hydrolyzable silicon group having a value of 3 (hereinafter referred to as “hydrolyzable silicon group (Z)”). In the composition of the present invention, the number of hydrolyzable silicon groups (Z) in the hydrolyzable silicon group represented by the general formula (1) can be changed according to the use, required characteristics, and the like.

When the polymer having a hydrolyzable silicon group represented by the general formula (1) is a polymer having only the hydrolyzable silicon group (Z) as the hydrolyzable silicon group,
That is, almost 100% of the hydrolyzable silicon group represented by the general formula (1) in the composition, that is, 80 to 10
When 0% is a hydrolyzable silicon group (Z), there is an effect that the curing rate is high, and a room-temperature curable composition having particularly excellent deep curability can be obtained. In this case, in particular, 90 to 100 of the hydrolyzable silicon group represented by the general formula (1) is used.
%, More preferably 95 to 100%, is preferably a hydrolyzable silicon group (Z).

When the hydrolyzable silicon group in which a in the general formula (1) is 1 or 2 and the hydrolyzable silicon group (Z) are mixed, good elongation characteristics and rapid curability are obtained. And a room-temperature-curable composition that is compatible with the above.

In this case, the proportion of the hydrolyzable silicon group (Z) in the total hydrolyzable silicon group represented by the general formula (1) is preferably 5 to 80%. By changing this ratio arbitrarily, the characteristics according to the requirements can be freely controlled.
That is, the ratio of the hydrolyzable silicon group (Z) is 5 to 50%.
At the same time, it is possible to improve the curability and at the same time to provide good elongation characteristics and flexibility required for a sealant or the like, and when the proportion of the hydrolyzable silicon group (Z) is 50 to 80%, The curability can be dramatically improved while ensuring sufficient elongation characteristics required for an adhesive or the like.

In the hydrolyzable silicon group represented by the general formula (1), the hydrolyzable silicon group other than the hydrolyzable silicon group (Z) is the hydrolyzable silicon group represented by the general formula (1) wherein a is 2 It is particularly preferred that it is a crystalline silicon group.

In order to obtain a composition in which a hydrolyzable silicon group (a) in the general formula (1) is 1 or 2 and a hydrolyzable silicon group (Z) are mixed, for example, the following method (e) , (F). The methods (e) and (f) may be used in combination.

(E) a hydrolyzable silicon group wherein a in the general formula (1) is 1 or 2, and a in the general formula (1) is 3
And a polymer having a hydrolyzable silicon group (Z). (F) A polymer having a hydrolyzable silicon group in which a in the general formula (1) is 1 or 2, and a polymer having a hydrolyzable silicon group (Z) in which a in the general formula (1) is 3 Use both coalescing.

The molecular weight of the polymer in the present invention is preferably selected from a range of 1,000 to 50,000 depending on the intended use. That is, for applications such as sealants where flexibility is important, the molecular weight calculated from the hydroxyl value of the polyoxyalkylene compound having a hydroxyl group as a raw material (hereinafter referred to as the hydroxyl value-converted molecular weight) is 4000.
~ 50,000 polymers are suitable. 6000-50,000
Is more preferable, and particularly preferably 8,000 to 25,000. For applications such as adhesives that require strength, the hydroxyl value-converted molecular weight is from 1,000 to 30,000.
Are suitable. When it is lower than 1,000, the cured product becomes brittle, and when it exceeds 50,000, the workability is remarkably deteriorated due to the high viscosity. It is more preferably from 3,000 to 20,000, particularly preferably from 6,000 to 20,000.

In the present invention, a curing catalyst (B) is essential for curing the polymer. When the curing catalyst (B) is not used, it is difficult to obtain a significant reaction rate in the crosslinking reaction of the hydrolyzable silicon group. As the amount of the curing catalyst used, the polymer (A)
It is preferably used in the range of 0.001 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight, per 100 parts by weight.

As the curing catalyst (B), salts of carboxylic acids of various metals such as alkyl titanate, organosilicon titanate, and dibutyltin dilaurate;
Acetylacetonate complexes, acetoacetate esterate complexes, various acid and base materials can be used. Specifically, metal salts such as tin 2-ethylhexanoate, lead 2-ethylhexanoate, dialkyltin dicarboxylate, and dibutyltin bisacetylacetonate, organic amines, dibutylamine-2-ethylhexoate, and the like. Amine salts and the like. These catalysts can be used alone or in combination.

In the present invention, the following silicon compound (C-
The silicon compound (C) comprising 1) and / or (C-2) is used. The following silicon compound (C) is indispensable for increasing the adhesive strength to an adherend and obtaining a composition that exhibits strong adhesive strength without a primer treatment.

Silicon compound (C): (C-1): a low molecular weight silicon compound having a hydrolyzable silicon group and a functional group represented by the general formula (2). (C-2): a reaction product obtained by reacting two or more low-molecular silicon compounds (C-1) each having a functional group that can react with each other, among the low-molecular silicon compounds (C-1). —SiX ¹ _b R ¹³ _-b (2) (In the general formula (2), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and X ¹ is a hydroxyl group or A hydrolyzable group, and b is 1, 2 or 3, provided that
When a plurality of R ¹ are present, they may be the same or different,
When a plurality of X ¹ are present, they may be the same or different. )

In the low molecular silicon compound (C-1), R
¹ is preferably a group selected from the same group as R described above. X ¹ is preferably a group selected from the same group as X described above. The low molecular silicon compound (C-1) may have at least one hydrolyzable silicon group represented by the formula (2), and preferably has one or two hydrolyzable silicon groups. The molecular weight of the low molecular weight silicon compound (C-1) is preferably 1,000 or less, more preferably 500 or less.

The functional group of the low molecular weight silicon compound (C-1) is a hydroxyl group, a mercapto group, an amino group, an epoxy group,
It is preferably a functional group selected from an acryloyloxy group, a methacryloyloxy group and a urethane group.
More preferably, it is a functional group selected from an amino group, an epoxy group, an acryloyloxy group and a methacryloyloxy group. The low molecular silicon compound (C-1) may have one or more functional groups, and may have two or more functional groups.

Examples of the silicon compound having an amino group include:
Silicon compounds having a primary amino group are preferred. Among them, compounds having both primary amino groups and secondary amino groups and / or tertiary amino groups are particularly preferred.

Examples of the silicon compound having an amino group include the following compounds. N- (β-aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, N- (β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane, N, N′-
Bis (γ-triethoxysilylpropyl) ethylenediamine, N-γ-trimethoxysilylpropyl-N′-β
-Aminoethyl-ethylenediamine H ₂ NCH ₂ CH ₂
NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH
₃ ) ₃ , N-γ-methyldimethoxysilylpropyl-
N'-β-aminoethyl-ethylenediamine H ₂ NCH
₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
_{(OCH 3) 2 (CH 3} ).

The following compounds are mentioned as the silicon compound having an epoxy group. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane.

The following compounds are mentioned as the silicon compound having an acryloyloxy group. γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-acryloyloxypropyltriethoxysilane.

Examples of the silicon compound having a methacryloyloxy group include the following compounds. γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane,
[gamma] -methacryloyloxypropyltriethoxysilane.

Examples of the silicon compound having a mercapto group include the following compounds. γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane.

Examples of the silicon compound having a urethane group include a modified isocyanate group of a silicon compound having an isocyanate group. That is, a reaction product of a silicon compound having an isocyanate group such as γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropylmethyldimethoxysilane with an active hydrogen compound such as ammonia, monoamine, polyamine, monol, polyol, and thioalcohol. It is. An allophanate-modified product or a burette-modified product may be used.

The low molecular silicon compound (C-1) is preferably the above-mentioned silicon compound having an amino group, silicon compound having an epoxy group or silicon compound having a methacryloyloxy group.

The low-molecular silicon compound (C-2) is obtained by reacting two or more low-molecular silicon compounds (C-1) having a functional group capable of reacting with each other among the low-molecular silicon compounds (C-1). This is a reaction product (C-2) obtained by the reaction.

Preferred is a combination of a silicon compound having an amino group and a silicon compound having an epoxy group or a methacryloyloxy group, which is a reaction product obtained by reacting an amino group with an epoxy group or a methacryloyloxy group. It is particularly preferred that there is.

In this reaction, a silicon compound having an epoxy group or a methacryloyloxy group is mixed at a ratio of 0.2 to 5 mol with respect to 1 mol of a silicon compound having an amino group in a nitrogen atmosphere at a temperature ranging from room temperature to 180 ° C. It is easily obtained by stirring.

The silicon compound (C) is a polymer (A) 1
It is used in an amount of 0.01 to 20 parts by weight based on 00 parts by weight.
If the amount is less than 0.01 part by weight, the expected adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected.

The compositions of the present invention may further include
Fillers, plasticizers, pigments, thixotropic agents, various anti-aging agents, ultraviolet absorbers, and the like can be used.

As fillers, calcium carbonate, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth,
Calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc flower, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, fir flour, graphite, aluminum fine Powdered fillers such as powder and flint powder, and fibrous fillers such as asbestos, glass fiber, glass filament, carbon fiber, Kevlar fiber, and polyethylene fiber can be used. The amount of the filler used is preferably 50 to 800 parts by weight based on 100 parts by weight of the polymer (A). Especially 50-250
Parts by weight are preferred.

Examples of the plasticizer include phthalic esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; aliphatic carboxylic esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate; Alcohol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxy stearate; chlorine Paraffins; polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyoxyalkylenes such as polyoxypropylene glycol and its derivatives; polystyrene such as poly-α-methylstyrene and polystyrene. Oligomer, polybutadienes, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, polymeric plasticizers oligomers such as epoxidized polybutadiene can be used. The amount of the plasticizer used is 10% for the polymer (A).
0 to 100 parts by weight relative to 0 parts by weight is preferred.

Examples of the pigment include inorganic pigments such as iron oxide, chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green. Zinc, fine powder silica, and the like.

The room temperature curable composition of the present invention can be used for sealants, waterproofing materials, adhesives, coating agents, etc.
In particular, it is suitable for applications that require sufficient cohesion of the cured product itself and dynamic followability to the adherend.

[0062]

EXAMPLES The present invention will be described below with reference to Production Examples (Examples 1 to 6), Examples (Examples 7 to 9 and Examples 13 to 15), Comparative Examples (Examples 10 to 12).
Examples 16 to 18) will be specifically described, but the present invention is not limited to these. Parts are parts by weight.

Example 1 Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol. Isocyanatepropyltrimethoxysilane was added thereto, and a urethanation reaction was performed to convert the terminal to a trimethoxysilyl group, thereby obtaining a polymer P1 having a molecular weight of 18,000.

Example 2 A polyoxypropylene diol having an average molecular weight of 3,000 obtained using a potassium hydroxide catalyst was reacted with chlorobromomethane in the presence of sodium metal to increase the molecular weight. After converting the obtained polyoxypropylene diol into sodium alkoxide, allyl chloride was reacted to obtain polyoxypropylene having an allyloxy group at a terminal. Trimethoxysilane is reacted as a hydrosilyl compound in the presence of a platinum catalyst to give a molecular weight of 900 having a trimethoxysilyl group at a terminal.
0 was obtained.

A terminal hydroxyl group of polyoxypropylene triol obtained by reacting propylene oxide with glycerin as an initiator using a potassium hydroxide catalyst is subjected to terminal allyloxylation in the same manner as described above, and then methyldimethoxysilane is used as a hydrosilyl compound. Was reacted in the presence of a platinum catalyst to obtain a polymer having a molecular weight of 6000 and having a methyldimethoxysilyl group at a terminal.

The polymer having a molecular weight of 9000 and a molecular weight of 60
The polymer No. 00 was mixed at a weight ratio of 60:40 to obtain a polymer mixture P2.

[Example 3] Propylene oxide was polymerized using propylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol. The terminal hydroxyl group of the obtained polyoxypropylene diol was subjected to terminal allyloxylation in the same manner as in Example 2, and then a mixture of trimethoxysilane and methyldimethoxysilane in a 70:30 weight ratio as a hydrosilyl compound was reacted in the presence of a platinum catalyst. Thus, a polymer P3 having a molecular weight of 12,000 and having both a trimethoxysilyl group and a methyldimethoxysilylpropyl group at a terminal was obtained.

[Example 4] Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol. Isocyanate propylmethyldimethoxysilane was added thereto, and a urethanation reaction was performed to convert both ends to a methyldimethoxysilylpropyl group, resulting in a molecular weight of 18,000.
A polymer P4 was obtained.

Example 5 A polyoxypropylene diol having an average molecular weight of 3000, obtained using a potassium hydroxide catalyst, was reacted with chlorobromomethane in the presence of sodium metal to increase the molecular weight. After the terminal hydroxyl group of the obtained polyoxypropylene diol was allyl-oxylated in the same manner as in Example 2, methyldimethoxysilane was reacted as a hydrosilyl compound in the presence of a platinum catalyst to give a molecular weight of 9000 having a methyldimethoxysilyl group at the terminal.
Was obtained.

The terminal hydroxyl group of polyoxypropylene triol obtained by reacting propylene oxide with glycerin as an initiator using a potassium hydroxide catalyst was subjected to terminal allyloxylation in the same manner as in Example 2, and then methyldimethoxy was used as a hydrosilyl compound. The silane was reacted in the presence of a platinum catalyst to obtain a polymer having a molecular weight of 6000 and having a methyldimethoxysilyl group at a terminal.

The polymer having a molecular weight of 9000 and a molecular weight of 60
The polymer No. 00 was mixed at a weight ratio of 60:40 to obtain a polymer mixture P5.

Example 6 Propylene oxide was polymerized using propylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol. The terminal hydroxyl group of the obtained polyoxypropylene diol was subjected to terminal allyloxylation in the same manner as in Example 2, and then methyldimethoxysilane was reacted as a hydrosilyl compound in the presence of a platinum catalyst to give a molecular weight of 12,000 having a methyldimethoxysilyl group at the terminal. A polymer P6 was obtained.

Examples 7 to 12 100 parts of the polymer (P1 to P6) obtained in Examples 1 to 6 were added to N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane
Parts, 1 part of γ-glycidyloxypropyltrimethoxysilane and dibutyltin dilaurate /
2 parts by weight of a 3/1 mixture of laurylamine are added,
A homogeneous mixture was prepared, and a sample was prepared by the method described below, and the change with time of the tensile shear strength was tracked. Table 1 shows the results.

<Measurement method of tensile shear strength> The above composition was applied between two aluminum plates having a width of 25 mm and thoroughly wiped with acetone so as to have a thickness of 1 mm and an adhesive area of 25 mm width × 25 mm length. After holding for a certain time, both ends of the two aluminum plates were pulled at a head speed of 50 mm, and the shear strength was measured.

[Examples 13 to 18] 100 parts of the polymers (P1 to P6) obtained in Examples 1 to 6 were added to calcium carbonate 10
0 parts, 2 parts of N- (β-aminoethyl) -γ-aminopropylmethyltrimethoxysilane, and 2 parts of a 3/1 mixture by weight of dibutyltin dilaurate / laurylamine as a curing catalyst to form a uniform mixture, A sample was prepared in the same manner as described above, and the change with time of the tensile shear strength was tracked. Table 2 shows the results.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

As described above, the room temperature curable composition of the present invention has a feature of being extremely excellent in curability.

Claims (6)

[Claims] 1. A room temperature curable composition containing a polymer having a hydrolyzable silicon group represented by the following general formula (1), wherein a in the general formula (1) is 3 (A), a curing catalyst (B) and the following low molecular silicon compound (C-1) and / or (C-2)
Room temperature curable composition containing a silicon compound (C) comprising: —SiX _a R _3-a (1) (In the general formula (1), R is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and X is a hydroxyl group or a hydrolyzable group. And a is 1, 2 or 3. However, when a plurality of Rs are present, they may be the same or different, and when a plurality of Xs exist, they may be the same or different.) Silicon compound (C ): (C-1): a low molecular weight silicon compound having a hydrolyzable silicon group and a functional group represented by the general formula (2). (C-2): a reaction product obtained by reacting two or more low-molecular silicon compounds (C-1) each having a functional group that can react with each other, among the low-molecular silicon compounds (C-1). —SiX ¹ _b R ¹³ _-b (2) (In the general formula (2), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and X ¹ is a hydroxyl group or A hydrolyzable group, and b is 1, 2 or 3, provided that
When a plurality of R ¹ are present, they may be the same or different,
When a plurality of X ¹ are present, they may be the same or different. ) 2. A polymer having both a hydrolyzable silicon group in which a is 1 or 2 in the general formula (1) and a hydrolyzable silicon group in which a is 3 in the general formula (1). The room temperature curable composition according to claim 1. 3. A polymer having a hydrolyzable silicon group wherein a in the general formula (1) is 1 or 2 and a polymer having a hydrolyzable silicon group wherein a in the general formula (1) is 3 The room temperature curable composition according to claim 1, which contains both of the following. 4. A polymer having a hydrolyzable silicon group represented by the general formula (1), wherein only the hydrolyzable silicon group in which a in the general formula (1) is 3 is used as the hydrolyzable silicon group. The room temperature-curable composition according to claim 1, which is a polymer having the same. 5. The room temperature curable composition according to claim 1, wherein the main chain of the polymer (A) is a polyoxyalkylene chain. 6. The polymer (A) according to claim 1, wherein the main chain is a polyoxyalkylene chain obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex as a catalyst. The room temperature curable composition according to the above.