JP2001072854A - Room temperature curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a polymer having a hydrolyzable silicon group obtained from a silane compound which can be easily handled industrially as a raw material, to have low viscosity, excellent handling properties, adhesion and mechanical properties. Provided is a curable composition which is excellent in physical properties of a cured product after curing such as strength and weather resistance, and furthermore, can adjust a curing speed in a wide range. SOLUTION: An unsaturated group is introduced into a terminal of a polyoxyalkylene polymer (A) having a hydrolyzable silicon group in which two hydrolyzable groups are bonded to silicon and a polyoxyalkylene polymer having a hydroxyl group. Thereafter, a polyalkylene polymer (B) having a hydrolyzable silicon group obtained by reacting a compound having a mercapto group with a hydrolyzable silicon group having three hydrolyzable groups bonded to silicon, and a polymerizable polymer A room temperature curable composition (D) containing a polymer (C) obtained by polymerizing an unsaturated group-containing monomer (E) as an essential component is used.

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 polyoxyalkylene polymer having a hydrolyzable silicon group at its terminal makes use of the characteristic that a cured product has rubber elasticity, and is used in applications such as sealants and adhesives, such as coating compositions and sealing compositions. Used. However, such a polyoxyalkylene polymer has adhesiveness, mechanical strength, weather resistance, or curability.
It also had insufficient points.

In order to solve these problems, for example, JP-A-59-78223 and JP-A-59-12
JP-A-2541, JP-A-60-31556 and JP-A-1-131271 disclose a polyoxyalkylene polymer having a reactive silicon group and an alkyl acrylate or / and methacrylate having a reactive silicon group. There is disclosed a method of improving weather resistance by mixing a polymer obtained by polymerizing a polymerizable monomer such as a polymerizable monomer. JP-A-6-172631 discloses a polyoxyalkylene polymer having a reactive silicon group and a narrow molecular weight distribution and a polymerizable monomer having a reactive silicon group such as an alkyl acrylate and / or an alkyl methacrylate. Discloses a method of mixing a polymer obtained by polymerizing a compound, which shows that a composition having a lower viscosity can be obtained and the curability can be improved as compared with the methods described above.

[0004] Further, Japanese Patent Application Laid-Open No. 5-1946 by the present applicant is disclosed.
No. 77 and JP-A-7-62219 disclose a method in which a vinyl monomer having a glycidyl group-containing monomer as an essential component is polymerized in the presence of a polyoxyalkylene polymer having a reactive silicon group. The disclosed polymers are disclosed and have been shown to improve adhesion and mechanical strength.

However, the reactive silicon group of the polyoxyalkylene polymer having a reactive silicon group used in these known methods is substantially only a methyldimethoxysilyl group, and has an adhesive property and a mechanical strength. Although the physical properties of the effected body after curing such as weather resistance can be improved, there are cases where the curability is insufficient for use in applications where faster curing is desired.

As a method for simultaneously solving these problems, Japanese Patent Application Laid-Open No. Hei 10-251552 discloses a polyoxyalkylene polymer having a trialkoxysilyl group at the molecular end and a polyoxyalkylene polymer having an alkyldialkoxy group at the molecular end. A composition comprising a polymer obtained by polymerizing a polymerizable monomer such as an alkyl acrylate and / or a methacrylic acid alkyl ester having a polyalkoxysilyl group is disclosed. In this method, a polymer obtained by a urethanization reaction between a polyoxypropylene polyol and an isocyanate-substituted trialkoxysilane compound is essentially used. In this method, the reactivity between the polyoxypropylene polyol and the isocyanate group is low, and in order to obtain a significant reaction rate, a reaction accelerator such as various metal salts well known in urethanization reaction for accelerating the reaction. Is desirable, in which case, due to the trace amount of water remaining in the reaction system,
In many cases, the alkoxysilyl groups undergo hydrolysis and cross-linking reactions, resulting in high viscosity of the polymer. Further, since the viscosity becomes high even due to the urethane bond itself, there is a problem in workability.

[0007] Japanese Patent Application No. Hei 10-98 filed by the present applicant.
No. 1803 describes a polyoxyalkylene polymer having a hydrolyzable silicon group and having a molecular weight of 8,000 to 50,000, wherein three hydrolyzable groups per silicon atom are essential as hydrolyzable silicon groups, A composition containing a polymer obtained by polymerizing a monomer has been filed.

In this method, as a polyoxyalkylene polymer having a hydrolyzable silicon group in which three hydrolyzable groups are bonded to one silicon atom, an unsaturated group is added to the end of the raw material polyoxyalkylene polymer. The polymer obtained by reacting the introduced polymer with trimethoxysilane, which is a hydrosilyl compound, is used. The trimethoxysilane, which is a hydrosilyl compound used here, is silane (SiH ₄ ). Due to disproportionation, the handling technology such as transfer and storage had great difficulties due to safety problems.

[0009] In this method, the hydrolysis and crosslinking reaction of the hydrolyzable silicon group proceed rapidly, so that the curing speed of the resin is increased, but the usable time, so-called open time, is too short. It had the disadvantage of being difficult to do. Adjustment of the curing speed, generally, various metal carboxylate having a catalytic action of the curing reaction,
It is known that it is possible to some extent by selecting types and amounts of basic and acidic compounds and the like, but it has not been possible to adjust freely so as not to be affected by the reactivity of the terminal. Also, industrially, it is required to be able to cope with various curing speeds, and a technique capable of freely controlling the curability has been required.

[0010]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to use a polymer having a hydrolyzable silicon group obtained from a silane compound which can be easily handled industrially, and to obtain a polymer having a low viscosity. Excellent handleability, and excellent cured physical properties after curing such as adhesion, mechanical strength, and weather resistance,
In addition, it is an object of the present invention to provide a curable composition whose curing speed can be adjusted over a wide range.

[0011]

That is, the present invention provides a polyoxyalkylene polymer (A) having a hydrolyzable silicon group represented by the following formula (1) and a polyoxyalkylene polymer having a hydroxyl group. A hydrolyzable silicon compound represented by the following formula (2) obtained by reacting the unsaturated group with a mercapto group of the silicon compound represented by the formula (3) after introducing an unsaturated group into the terminal of Room temperature curable composition (D) comprising, as essential components, a polyoxyalkylene polymer having a group (B) and a polymer (C) obtained by polymerizing a polymerizable unsaturated group-containing monomer (E). Is provided.

--SiX ₂ R ¹ (1) (In the formula (1), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, However, two Xs may be the same or different.) -SiX ₃ (2) (In the formula (2), X is the same as above. Three Xs may be the same or different.) HS—R ² —SiX ₃ (3) (In the formula (3), X is the same as above. Three Xs may be the same or different. R ² is a divalent carbon having 1 to 17 carbon atoms.) Hydrogen group.)

[0013]

DETAILED DESCRIPTION OF THE INVENTION (Polyoxyalkylene polymer)
The polyoxyalkylene polymer (A) having a hydrolyzable silicon group represented by the above formula (1) used in the present invention and the polyoxyalkylene having a hydrolyzable silicon group represented by the above formula (2) As described below, the polymer (B) is produced by using a polyoxyalkylene polymer having a functional group as a raw material, and introducing a hydrolyzable silyl group through an organic group to part or all of the terminal thereof. It is preferable to use, for example, those described in JP-A-3-47825, JP-A-3-72527, and JP-A-3-79627. (Raw material polyoxyalkylene polymer) As the raw material polyoxyalkylene polymer of the polyoxyalkylene polymers (A) and (B), in the presence of a catalyst and in the presence of an initiator,
Hydroxyl terminal ones produced by reacting a cyclic ether or the like are preferred. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used. Examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and tetrahydrofuran. 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.

In the present invention, it is preferable to use a high molecular weight polyoxyalkylene polymer having a molecular weight of 8,000 to 50,000 as the starting polyoxyalkylene polymer. Therefore, a polyoxyalkylene polymer or a complex metal cyanide complex catalyst obtained by reacting a polyoxyalkylene polymer having a relatively low molecular weight produced using an alkali catalyst or the like with a polyhalogen compound such as methylene chloride to obtain a large amount is obtained. It is preferable to use a polyoxyalkylene polymer produced using the method.

It is particularly preferable to use a polyoxyalkylene polymer having a weight average molecular weight (Mw) and a number average molecular weight (Mn) ratio Mw / Mn of 1.7 or less.
Mw / Mn is more preferably 1.6 or less,
Mw / Mn is particularly preferably 1.5 or less. The polyoxyalkylene polymers (A) and (B) can be obtained by using such a polyoxyalkylene polymer as a raw material and further modifying a terminal group to obtain a hydrolyzable silicon group.

When the viscosity of the raw material polyoxyalkylene polymer is adjusted to a certain level, Mw / Mn
The smaller the is, the lower the content of the low molecular weight polymer is. As a result, the polyoxyalkylene polymer having a hydrolyzable silicon group obtained by using this as a raw material has M
As compared with the case where the raw material having a large w / Mn is used as a raw material, the curability is excellent such as improved deep curability at the time of curing, and the cured product obtained by curing has the same elastic modulus as the cured product. High elongation and high strength.

Further, when compared with starting polyoxyalkylene polymers having the same number average molecular weight (Mn) but different Mw / Mn, the smaller the Mw / Mn, the lower the viscosity of the polymer and the better the workability. Having. From the viewpoint of obtaining such a raw material polyoxyalkylene polymer having a small Mw / Mn, a compound obtained by polymerizing a cyclic ether in the presence of an initiator using a double metal cyanide complex as a catalyst is particularly preferable.

The complex metal cyanide complex is preferably a complex mainly composed of zinc hexacyanocobaltate.
Of these, ether and / or alcohol complexes are preferred. Its composition can be essentially the one described in JP-B-46-27250. Specifically, the ether is preferably ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) or the like. Grime is particularly preferred from the viewpoint of handling. In addition, t-butanol is preferable as the alcohol.

The number of functional groups in the starting polyoxyalkylene polymer is preferably 2 or more. When it is desired to increase flexibility as a cured product property, the number of functional groups of the starting polyoxyalkylene polymer is particularly preferably 2 or 3. In order to obtain good adhesiveness and curability, the number of functional groups of the starting polyoxyalkylene polymer is particularly preferably 3 to 8. As the raw material polyoxyalkylene polymer, specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene and 2
And copolymers of at least one kind of cyclic ether.

Particularly preferred raw material polyoxyalkylene polymers are di- to hexavalent polyoxypropylene polyols, particularly polyoxypropylene diol and polyoxypropylene triol. In addition, the following (a) and (d)
In the above method, an unsaturated group-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monol can also be used. (Polyoxyalkylene polymer (A)) The polyoxyalkylene polymer (A) has a hydrolyzable silicon group represented by the following formula (1) at a terminal or a side chain of a molecular chain.

--SiX ₂ R ¹ (1) (In the formula (1), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, However, two X's may be the same or different.) Equation (1)
Wherein R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group, particularly preferably a methyl group, an ethyl group, Group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like. R
^{When 1} is present in plurality may or may not be those R ¹ same.

Examples of the hydrolyzable group for X include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, a carbamoyl group, an amino group, an aminooxy group, a ketoximate group and the like. Among these, the carbon number of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred examples of X include an alkoxy group and an alkenyloxy group having 4 or less carbon atoms, in particular, a methoxy group, an ethoxy group, a propoxy group and a propenyloxy group.

That is, the hydrolyzable silicon group represented by the following formula (1) is particularly preferably a structure having an alkyldialkoxysilyl group having an alkoxy group having 4 or less carbon atoms. A dimethoxymethylsilyl group is most preferred. The hydrolyzable silicon group represented by the formula (1) is usually introduced into a raw material polyoxyalkylene polymer via an organic group. That is, the polyoxyalkylene polymer (A) preferably has a group represented by the formula (4).

-R ⁰ -SiX ₂ R ¹ (4) (In the formula (4), R ⁰ is a divalent organic group, and R ¹ and X are the same as above.) To the raw material polyoxyalkylene polymer The method of introducing the hydrolyzable silicon group is not particularly limited, but can be introduced by, for example, the following methods (a) to (d). (A) A method in which an unsaturated group is introduced into a terminal of a polyoxyalkylene polymer having a hydroxyl group, followed by reaction with a hydrosilyl compound represented by the formula (5).

HSiX ₂ R ¹ (5) (In the formula (5), R ¹ and X are the same as described above.) As a method for introducing an unsaturated group, a compound having an unsaturated group and a functional group is used. By reacting with a terminal hydroxyl group of a polyoxyalkylene polymer having a hydroxyl group, an ether bond,
Examples of such a method include a method of bonding by an ester bond, a urethane bond, a carbonate bond, or the like. As the unsaturated group referred to herein, CH ₂ ＣＨCH—R ′ — (R ′ has 1 carbon atom)
To 18 divalent hydrocarbon groups). R ′ is preferably a hydrocarbon group having 1 to 5 carbon atoms. As the unsaturated group, an allyl group is particularly preferred. As the compound having an unsaturated group and a functional group, allyl chloride is particularly preferable, and by using this, the hydroxyl group of the polyoxyalkylene polymer having a hydroxyl group can be converted to an allyloxy group. When polymerizing an alkylene oxide, a method of adding an unsaturated group-containing epoxy compound such as allyl glycidyl ether and copolymerizing the same to introduce an unsaturated group into the side chain of the raw material polyoxyalkylene polymer can also be used.

When reacting the hydrosilyl compound, a platinum catalyst, a rhodium catalyst, a cobalt catalyst,
A catalyst such as a palladium-based catalyst or a nickel-based catalyst can be used. Platinum-based catalysts such as chloroplatinic acid, platinum metal, platinum chloride, and platinum-olefin complexes are preferred. Further, the reaction for reacting the hydrosilyl compound is preferably performed at a temperature of 30 to 150 ° C., preferably 60 to 120 ° C. for several hours.

(B) A method of reacting a compound represented by the formula (6) with a terminal of a polyoxyalkylene polymer having a hydroxyl group. R ¹ —SiX ₂ —R ² NCO (6) (In the formula (6), R ¹ and X are the same as above. R ² has 1 carbon atom.
To 17 divalent hydrocarbon groups. In the above reaction, a known urethanation catalyst may be used. The above reaction is 20-
It is preferably carried out at a temperature of 200 ° C., preferably 50 to 150 ° C. for several hours.

(C) A terminal of the polyoxyalkylene polymer having a hydroxyl group is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, and the silicon compound represented by the formula (7) is added to the isocyanate group. Reacting the W group of R ¹ —SiX ₂ —R ² W (7) (In the formula (7), R ¹ , R ² , and X are the same as above. W represents a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (1
Active hydrogen-containing group selected from primary or secondary). (D) After introducing an unsaturated group into the terminal of the polyoxyalkylene polymer having a hydroxyl group, the unsaturated group is reacted with a mercapto group of a silicon compound represented by the formula (7) wherein W is a mercapto group. How to let.

The method for introducing an unsaturated group and the unsaturated group are as follows:
This is the same as that described in (a). Examples of the silicon compound represented by the formula (7) wherein W is a mercapto group include 3-mercaptopropylmethyldimethoxysilane.

In the above reaction, a polymerization initiator such as a radical generator may be used, and in some cases, the reaction may be performed by radiation or heat without using a polymerization initiator. Examples of the polymerization initiator include a peroxide-based, azo-based, or redox-based polymerization initiator and a metal compound catalyst. Specifically as the polymerization initiator,
Examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2methylbutyronitrile), benzoyl peroxide, t-butyl peroxide, acetyl peroxide, and diisopropyl peroxydicarbonate. The reaction is preferably carried out at 20 to 200 ° C, preferably 50 to 150 ° C, for several hours to several tens hours. (Polyoxyalkylene polymer (B)) The polyoxyalkylene polymer (B) has a hydrolyzable silicon group represented by the following formula (2) at a terminal or a side chain of a molecular chain.

--SiX ₃ ... (2) (In formula (2), X is the same as above. Three Xs may be the same or different.) Hydrolyzable group in X in formula (2) Examples of the same include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, a carbamoyl group, an amino group, an aminooxy group, a ketoximate group, and the like.

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. Preferred examples of X include an alkoxy group and an alkenyloxy group having 4 or less carbon atoms, in particular, a methoxy group, an ethoxy group, a propoxy group and a propenyloxy group. That is, the hydrolyzable silicon group represented by the following formula (2) is particularly preferably a structure having a trialkoxysilyl group having an alkoxy group having 4 or less carbon atoms. Trimethoxysilyl groups are most preferred.

The polymer having a trialkoxysilyl group has a very high reactivity, and particularly has a very high initial curing rate. Usually, in the hydrolysis reaction, the silanol groups produced by reaction with water (-SiX + H ₂ O → -SiOH
+ HX), and the resulting silanol groups are considered to proceed by condensation or by condensation between the silanol group and the hydrolyzable silicon group to form a siloxane bond (condensation reaction). Once the silanol group is generated, the condensation reaction is considered to proceed smoothly. The trialkoxysilyl group has an extremely high reaction rate in the initial stage of the silanol group generation reaction as compared to the alkyl dialkoxysilyl group or the dialkylalkoxysilyl group. Therefore, it is considered that the curable composition of the present invention exhibits sufficient strength characteristics in a short time, and particularly has an effect of shortening the time until the adhesiveness is exhibited.

Among trialkoxysilyl groups, trialkoxysilyl groups having an alkoxy group having a small number of carbon atoms have a higher reaction rate in the initial stage of silanol group generation reaction than trialkoxysilyl groups having an alkoxy group having a large number of carbon atoms. Are more preferable, and a trimethoxysilyl group or a triethoxysilyl group is more preferable, and a trimethoxysilyl group is most preferable because a reaction rate in an initial stage of a silanol group generation reaction is extremely high.

In the polymer (B), similarly to the polymer (A), the hydrolyzable silicon group represented by the formula (2) is introduced into the raw material polyoxyalkylene polymer via an organic group. Is preferred. That is, the polyoxyalkylene polymer (B) preferably has a group represented by the formula (8). —Y—S—R ² —SiX ₃ (8) (In the formula (8), X is the same as above. Three Xs may be the same or different. Y is a divalent carbonization of 1 to 17) A hydrogen group, R ² is a divalent hydrocarbon group having 1 to 17 carbon atoms.) Y is preferably a hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a trimethylene group. R ² is preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a trimethylene group.

The polyoxyalkylene polymer (B) is obtained by introducing an unsaturated group into a terminal of a polyoxyalkylene polymer having a hydroxyl group, and then adding the unsaturated group to a mercapto group of a silicon compound represented by the formula (3). Is obtained by reacting HS-R ² —SiX ₃ (3) (In the formula (3), X is the same as above. Three Xs may be the same or different. R ² is a divalent carbon having 1 to 17 carbon atoms.) Hydrogen group.) For details of the introduction method, the method of introducing a hydrolyzable silicon group of the polyoxyalkylene polymer (A) (d).
This is the same as described above. As the unsaturated group, CH ₂ ＣＨCH—R′— (R ′ is the same as described above)
Is preferred.

Examples of the silicon compound represented by the formula (3) include 3-mercaptopropyltrimethoxysilane,
And mercaptopropyltriethoxysilane. The polyoxyalkylene polymer obtained by the above method has a characteristic that the curing speed is high, and has a characteristic that it has low viscosity and excellent workability. Further, raw materials are easily available, and are industrially useful.

The molecular weight of the polyoxyalkylene polymers (A) and (B) in the present invention can be selected from appropriate values depending on the intended use.
It is preferable that Polymers having a molecular weight of 8,000 to 50,000 are preferred for applications such as sealants where flexibility is important. The molecular weight is particularly preferably from 10,000 to 25,000, and most preferably from 12,000 to 20,000.

On the other hand, for applications such as adhesives that require a high elastic modulus, it is preferable that the molecular weight is smaller than that of the above applications in order to increase the number of terminals of the cross-linking group. In addition, in applications for adhesives, non-plastic blends that do not use a plasticizer are often used, and therefore it is generally preferable to have a low viscosity, and therefore it is preferable to have a smaller molecular weight. Specifically, a polymer having a molecular weight of 6,000 to 30,000 is preferred. When it is lower than 6000, the cured product becomes brittle, and when it exceeds 30,000, the workability is remarkably deteriorated due to the high viscosity. The molecular weight is particularly preferably from 6,000 to 20,000.

Although the above description has been made from the viewpoint of molecular weight, when these polymers are actually used in each application, there is a preferable polymer viscosity for use depending on each application. The molecular weight of the polymer is often determined from the viewpoint of coalescence viscosity. If the viscosity of the polymer is too high, the handling becomes difficult. If the viscosity is low, the properties of the cured product such as tensile strength and elongation at break generally deteriorate. Specifically, in applications such as sealants, it is preferably 60 poise to 400 poise at room temperature, and in applications such as adhesives, it is 25 poise at room temperature.
It is preferably 0 poise or less. (Polymer (C) Obtained by Polymerizing Polymerizable Unsaturated Group-Containing Monomer (E)) The room temperature curable composition (D) of the present invention comprises a polymerizable unsaturated group-containing monomer (E). The polymer (C) obtained by polymerizing is contained.

By containing the polymer (C), various characteristics can be imparted to the cured product after curing, such as improvement in mechanical strength, adhesion to a substrate, and weather resistance. . Further, a feature that the adhesive strength to the base material in the early stage of curing is improved as compared with the case where the polymer (C) is not contained is recognized. (Polymerizable unsaturated group-containing monomer (E)) Typical examples of the polymerizable unsaturated group-containing monomer (E) include compounds represented by the following formula (9). It is not limited to.

CRR ⁵ = CR ³ R ⁴ (9) (In the formula, R, R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a monovalent organic group.) The organic group for R and R ⁵ is preferably a monovalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. R and R ⁵ are more preferably each a hydrogen atom. The organic group in R ³ and R ⁴ is a group having 1 to 10 carbon atoms.
Substituted or unsubstituted hydrocarbon group, alkoxy group, carboxyl group, alkoxycarbonyl group, cyano group, cyano group-containing group, alkenyl group, acyloxy group, carbamoyl group, pyridyl group, glycidyloxy group or glycidyloxycarbonyl group Preferably, there is. R ³
Is particularly preferably a hydrogen atom, a halogen atom or a monovalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.

When a monomer (G) having both a polymerizable unsaturated group and a glycidyl group is used as a part or all of the polymerizable unsaturated group-containing monomer (E), excellent adhesion and mechanical properties can be obtained. It is preferable because a cured product having strength can be obtained. Specifically, unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether; unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl cinnamate, and glycidyl vinyl benzoate; Glycidyl esters, monoalkyl monoglycidyl esters or unsaturated glycidyl esters of unsaturated dicarboxylic acids are preferred. Of these, vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate are particularly preferred, and glycidyl methacrylate is most preferred.

When using the curable composition (D) containing the polymer (C) obtained by using the monomer (G) for a part or all of the monomer (E), an epoxy compound is generally used. It is preferable to use a compound used as a resin curing agent in combination, since a cured product having particularly excellent adhesiveness and mechanical strength can be obtained. Examples of such compounds include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as metaphenylenediamine,
Secondary amines, tertiary amines such as tris (dimethylaminomethyl) phenol, tertiary amine salts, acid anhydrides,
Examples include polyamide resins, polysulfide resins, boron trifluoride complex compounds, imidazoles, dicyandiamides, and the like.

Further, compounds such as ketimines and silazanes represented by the following formulas (10) and (11) can also be used. ^{R 6 R 7 C = N-} R 8 -NH-R 9 -N = CR 10 R 11 ··· (10) ( ^{wherein, R 6, R 7, R} 10, R 11 is a hydrogen atom, a halogen atom or monovalent hydrocarbon radicals .R ^8, R ⁹ is a divalent hydrocarbon ^{group.) R 12 R 13 C =} N-R 14 -N = CR 15 R 16 ··· (11) ( wherein, R ¹² , R ¹³ , R ¹⁵ , and R ¹⁶ are a hydrogen atom, a halogen atom or a monovalent hydrocarbon group. R ¹⁴ is a divalent hydrocarbon group. Styrene oxide, butyl glycidyl ether, γ-
Glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-
Compounds reacted with an epoxy group-containing compound such as glycidyloxypropyltriethoxysilane or a monoisocyanate compound such as phenyl isocyanate can also be used.

In the present invention, the curable composition (D) containing the polymer (C) obtained by using the monomer (G) for part or all of the monomer (E) is used. When a compound containing at least one functional group capable of reacting with an epoxy group or at least one epoxy group and at least one reactive silyl group in a molecule is used in combination, a cured product having more excellent adhesion and mechanical strength is obtained. It is preferable because it can obtain.
Specific examples of the compound containing at least one epoxy group and at least one reactive silyl group in the molecule include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyl Oxypropyltriethoxysilane and the like can be exemplified. Examples of the compound containing at least one functional group capable of reacting with an epoxy group and at least one reactive silyl group in a molecule include, specifically, 3-aminopropyltrimethoxysilane and 3- (2- Aminoethyl) aminopropyltrimethoxysilane, 3- (2-
Amino group-containing silanes such as aminoethyl) aminopropylmethyldimethoxysilane, 1,4-di (triethoxysilylpropyl) ethylenediamine, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Mercapto group-containing silanes such as dimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β
Carboxyl group-containing silanes such as-(N-carboxymethylaminoethyl) -γ-aminopropyltrimethoxysilane; These compounds can be used alone or
More than one species may be used in combination.

At least one monomer (H) selected from alkyl acrylate and / or alkyl methacrylate monomers may be used as a part or all of the polymerizable unsaturated group-containing monomer (E). Is preferred because a cured product having excellent weather resistance can be obtained. As the monomer (H), a compound represented by the following formula (12) is preferable.

[0048] _{^{CH 2 = CR 17 COOR 18 ···}} (12) ( wherein, R ¹⁷ is a hydrogen atom or a methyl group, R ¹⁸ represents a hydrogen atom or a monovalent organic group.) Further, R ¹⁸ is, Those having a hydrogen atom or an alkyl group having 1 or more carbon atoms are preferable, and particularly, an alkyl acrylate and / or methacrylic acid alkyl ester monomer (I) having an alkyl group having 1 to 8 carbon atoms and a C 10 -C 10
It is preferable to contain both of the above-mentioned alkyl acrylate alkyl ester and / or methacrylic acid alkyl ester monomer (J).

The alkyl acrylate and / or the methacrylate are referred to as alkyl (meth) acrylate. The monomer (I) preferably has an alkyl group having 1 to 4 carbon atoms. Specifically, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2
-Ethylhexyl, benzyl (meth) acrylate, etc., with methyl (meth) acrylate and butyl (meth) acrylate being particularly preferred. The monomers (I) may be used alone or in combination of two or more.

The above monomer (J) has 10 to 10 carbon atoms.
Those having an alkyl group of 30 are preferable and have 10 carbon atoms.
Those having from 20 to 20 alkyl groups are more preferred. Specifically, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, (meth)
And stearyl acrylate. The monomers (J) may be used alone or in combination of two or more.

The ratio of the above monomer (I) and the above monomer (J) can be arbitrarily adjusted, but the ratio by weight is 95/5 to 40/40.
60 is preferable, and 90/10 to 40/60 is more preferable. Some or all of the polymerizable unsaturated group-containing monomer (E) may have a polymerizable unsaturated group and a compound represented by formula (1) and / or formula (2).
Having a hydrolyzable silicon group (K)
When a is used, a hydrolyzable silicon group derived from the polyoxyalkylene polymer (A) or (B) and a polymerizable unsaturated group-containing monomer part or all of which is the monomer (K) It is preferable because a bond is formed at the time of curing between the hydrolyzable silicon groups derived from the polymer (C) obtained by polymerizing (E) and a cured product having extremely excellent mechanical strength can be obtained.

As such a monomer (K), a compound represented by the following formula (13) is particularly preferable. During ^{_{R 19 -SiX a R 1 3-}} a ··· (13) ( Equation (7), R ¹⁹ is a monovalent organic group having a polymerizable unsaturated group, R ^1, X are as defined above. a is 2 or 3. However, when a plurality of Xs are present, those Xs may be the same or different.) As the compound represented by the formula (13), the compound represented by the formula (1) and / or Examples include a vinyl monomer having a hydrolyzable silicon group represented by the formula (2) and an acrylic monomer having a hydrolyzable silicon group represented by the formula (1) and / or (2). . Specific examples include the following, and 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane are particularly preferable.

Vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane,
Vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, tris (2-methoxyethoxy) vinylsilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane,
3-acryloyloxypropyltrimethoxysilane,
3-acryloyloxypropyltriethoxysilane,
Acryloyloxysilanes such as 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane, and methacryloyloxysilanes.

In addition to these, for example, when a silicon atom is
A polysiloxane compound having from 30 to 30 and having both a carbon-carbon double bond and a silicon atom bonded to a hydrolyzable group represented by the formula (1) and / or the formula (2) can also be used. One of the above polymerizable monomers (K) may be used alone, or two or more thereof may be used in combination.

When the polymerizable monomer (K) is used, the polymerizable monomer (K) is a polymerizable unsaturated group-containing monomer (E) 100
It is preferable to use 0.01 to 20 parts by weight based on parts by weight.
Other examples of the polymerizable unsaturated group-containing monomer (E) include styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; and cyano group-containing such as acrylonitrile and 2,4-dicyanobutene-1. Monomers; vinyl ester monomers such as vinyl acetate and vinyl propionate; diene monomers such as butadiene, isoprene and chloroprene; and other olefins, unsaturated esters, halogenated olefins, vinyl ethers and the like. No. These monomers may be used alone or in combination of two or more.

In the radical polymerization reaction of the polymerizable unsaturated group-containing monomer (E) as described above, a compound known as a chain transfer agent can be used for the purpose of controlling the molecular weight and the like. As the chain transfer agent, generally known chain transfer agents such as a radical polymerization reaction can be used. Are preferred.

Further, when a compound having a hydrolyzable silyl group is used as the chain transfer agent, it is more preferable since the hydrolyzable silyl group can be introduced into the polymer (C). By introducing a hydrolyzable silyl group into the polymer (C), a bond is generated at the time of curing between the polyoxyalkylene polymer (A) and the hydrolyzable silicon group derived from the polymer (B). The physical properties of the cured product such as the strength and weather resistance of the cured product are further improved. As a method for introducing a hydrolyzable silyl group into the polymer (C),
A polymerizable unsaturated group and a hydrolyzable silicon group represented by the formula (1) and / or the formula (2) are partially or entirely provided with the polymerizable unsaturated group-containing monomer (E). It can also be introduced by using a monomer (K) having the same, but when a compound having a hydrolyzable silyl group is used as a chain transfer agent, a hydrolyzable silicon group is added to the terminal of the polymer (C). Since it can be selectively introduced into the cured product, the cured product after curing has excellent elongation characteristics.

Specific examples of such compounds include:
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriisopropenyloxysilane, etc. And a mercaptan compound having γ-mercaptopropyltrimethoxysilane. Further, as another example, (CH ₃ O) ₃ Si—S—S
—Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ Si— (C
_{H 2) 3 -S-S- (} CH 2) 3 -Si (OCH 3) 3
And the like.

In the polymerization of the polymerizable unsaturated group-containing monomer (E), a polymerization initiator such as a radical generator may be used. In some cases, radiation or heat may be used without using a polymerization initiator. It may be polymerized. The polymerization initiator, the polymerization temperature, the polymerization time, and the like are the same as those described in the above (d). (Room temperature curable composition (D)) The room temperature curable composition (D) of the present invention comprises a polyoxyalkylene polymer (A) having a hydrolyzable silicon group represented by the formula (1), and After introducing an unsaturated group into the terminal of the polyoxyalkylene polymer having a hydroxyl group, the above-mentioned formula (2) obtained by reacting the unsaturated group with the mercapto group of the silicon compound represented by the above formula (3) And a polymer (C) obtained by polymerizing a polymerizable unsaturated group-containing monomer (E) having a hydrolyzable silicon group represented by the following formula (B). It can be manufactured by the following methods (e) to (h).

(E) Polyoxyalkylene polymer (A)
And / or (B) and a polymer (C) obtained by previously polymerizing the polymerizable unsaturated group-containing monomer (E). (F) After polymerizing the polymerizable unsaturated group-containing monomer (E) in the polyoxyalkylene polymer (A) and / or (B), the polyoxyalkylene polymer (A) And / or (B).

(G) Polyoxyalkylene polymer (A)
And / or after polymerizing the polymerizable unsaturated group-containing monomer (E) in the precursor (F) of (B), the precursor (F)
Is a polyoxyalkylene polymer (A) and / or (B)
And optionally mixing with the polyoxyalkylene polymer (A) and / or (B) if necessary. Examples of the precursor (F) include a polyoxyalkylene polymer having a hydroxyl group and a polyoxyalkylene polymer having an unsaturated group.

As the conversion method, the same method as described in the method for introducing a hydrolyzable silicon group in the description of the polyoxyalkylene polymers (A) and (B) can be used. (H) After polymerizing the polymerizable unsaturated group-containing monomer (E) in the presence of a solvent or a diluent, and mixing with the polyoxyalkylene polymers (A) and (B), Then, the solvent or diluent is distilled off.

The solvent is a polymerizable unsaturated group-containing monomer (E)
Can be selected as appropriate according to the type of. As the diluent, a polyoxyalkylene polymer having an unsaturated group is preferable. During the polymerization, a polyoxyalkylene polymer having an unsaturated group may be present in a solvent or a diluent. The ratio of the polyoxyalkylene polymers (A) and (B) and the polymer (C) in the room temperature-curable composition (D) of the present invention may be arbitrarily selected according to the use and the required properties. Can be.

The ratio between the polyoxyalkylene polymers (A) and (B) is arbitrary, but the weight ratio of (A) :( B)
= 5 to 95:95 to 5, more preferably (A):
(B) = 20 to 80: preferably 80 to 20, (A):
(B) = 30 to 70: 70 to 30 is most preferable. That is, by arbitrarily adjusting the ratio of the polyoxyalkylene polymers (A) and (B), the curability can be adjusted in a wide range. Specifically, as the proportion of the polyoxyalkylene polymer (B) is increased, the curability can be increased, and by decreasing the proportion of the polyoxyalkylene polymer (B), the same curing can be achieved as before. It is possible to obtain a composition having an arbitrary curability up to a composition close to the curability. When a material having a large proportion of the polyoxyalkylene polymer (B) is used as an adhesive or a sealing material, the curability is fast, so that the effect of rapidly developing the adhesive strength after construction is obtained. In the usage method where the adherend must be fixed so that it does not move until the adhesiveness is developed, or when you want to adhere in a short time, or when you want to speed up the effect at low temperatures Useful.

On the other hand, with respect to the elongation characteristics of the cured product, the larger the proportion of the polyoxyalkylene polymer (A) is, the better it is. Therefore, the polyoxyalkylene polymer (A) and It is important to obtain the optimum composition at any time by arbitrarily changing the proportion of (B). Also, a polyoxyalkylene polymer (A)
And the ratio of (B) to the polymer (C) is in a range where the weight ratio of the total amount of the polyoxyalkylene polymers (A) and (B) / the polymer (C) is 100/1 to 1/300. It is preferable to use them. It is particularly preferable to use it in the range of 100/1 to 1/100, more preferably 100/1 to 1/10 in terms of workability and the like.

The polymer (C) may be uniformly dispersed or dissolved in the form of fine particles in the polyoxyalkylene polymer (A) and / or (B). In consideration of the viscosity and workability of the composition, it is preferable that the composition is uniformly dispersed in fine particles. The room temperature curable composition (D) of the present invention is not essential, but may or may not contain the following additives. Hereinafter, the additives will be described. (Filler) As the filler, a known filler can be used.
The amount of the filler used is a polyoxyalkylene polymer (A),
0.001 to 1000 parts by weight, particularly preferably 50 to 250 parts by weight, based on 100 parts by weight of the total of (B) and the polymer (C). The following are specific examples of the filler. These fillers may be used alone or in combination of two or more.

Heavy calcium carbonate having an average particle size of 1 to 20 μm, light calcium carbonate having an average particle size of 1 to 3 μm produced by a precipitation method, colloidal calcium carbonate having a surface treated with a fatty acid or a resin acid-based organic substance, light carbonic acid Calcium carbonates such as calcium, fumed silica, precipitated silica, surface siliconized silica fine powder, 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, resin beads, wood flour, pulp, cotton chips,
Powdered fillers such as mica, walnut flour, fir flour, graphite, aluminum fine powder and flint powder. asbestos,
Fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber and polyethylene fiber.

Further, a known inorganic or organic hollow body can be used. Since the hollow body has a low specific gravity, workability is improved, such as reducing the weight of the composition and the cured product thereof and improving the stringiness of the composition. Examples of the inorganic hollow body include a silicate-based hollow body and a non-silicate-based hollow body. Examples of the silicate-based hollow body include a shirasu balloon, a pearlite, a glass balloon, a silica balloon, and a fly ash balloon. Examples of the system hollow body include an alumina balloon, a zirconia balloon, and a carbon balloon. A shirasu balloon and a glass balloon are particularly preferable, and a glass balloon is most preferable.

Average particle diameter and average particle density of glass balloon
There is no particular limitation on the average particle size is usually 10 to 500
μm, preferably about 30-100 μm, average particle
Density: about 0.1 to 0.6 g / cc, preferably 0.15
~ 0.3g / cc, hako density 0.05 ~ 0.5g / c
c, preferably about 0.07 to 0.3 g / cc,
Pressure strength 10-1000kg / cm^TwoDegree, preferably 1
5 to 300 kg / cm ^TwoAbout 90% of hako capacity
Is common. Especially limited to the shape of glass balloon
No, but the closer to a sphere, the lower the viscosity of the composition
This is preferred.

Examples of the organic hollow body include a hollow body of a thermosetting resin and a hollow body of a thermoplastic resin. Examples of the hollow body of the thermosetting resin include a phenol balloon, an epoxy balloon, and a urea balloon. Examples of the hollow body of the plastic resin include a Saran balloon, a polystyrene balloon, a polymethacrylate balloon, a polyvinyl alcohol balloon, and a styrene-acrylic balloon. Further, a hollow body of a thermoplastic resin whose surface is coated with a thermosetting resin, or a hollow body of a crosslinked thermoplastic resin can be used. As the particles, besides the so-called hollow body, porous hollow particles having pores may be mentioned, and may be foamed in advance, or may be foamed after blending a foam containing a foaming agent.

When an organic hollow body is used, a curable composition having a characteristic of having a low modulus and excellent elongation in the tensile properties of a cured body after curing, in addition to an effect of reducing the weight of the composition and its cured body, Can be obtained. In addition, a hybrid type hollow body in which the surface of an organic hollow body is coated with an inert inorganic powder is also mentioned. Specifically, the surface of a hollow body mainly composed of polyacrylonitrile is made of calcium carbonate, talc, titanium, or the like. Those coated with powder are preferred because of their good compatibility with other fillers.

Specific examples of the inorganic hollow body include, for example, winlite (Ichi Kasei) as a shirasu balloon, Scotchlite glass bubbles (3M), CEL-STAR (Tokai Kogyo), and MICRO as a glass balloon. BALLON (EMERSON
& CUMING), CELAMIC GLASS M
ODULES (PITTSBURGH CORNING
CORP. ), Etc., as CEROSPHARES (PFA MARKETING
LTD. ), FILLITE (FILLITE U.).
S. A. INC. BW (Showa Denko) as an alumina balloon and HOL as a zirconia balloon.
LOW ZIRCONIUM SPHERES (ZIR
COA), etc., and carbon balloons such as Crecus Fair (Kureha Chemical) and Carbosphere (GENERAL T)
ECHNOLOGIES CORP. ) And the like.

As a specific example of the organic hollow body, for example, Phenolic M is used as a phenol balloon.
ICROBALLONS (UCC) and the like use ECCOSPHERES EP (EME) as an epoxy balloon.
RSON & CUMING) and others as ECCOSPHERES VF-0 (EMERSO) as a urea balloon.
N & CUMING) and others
ARAN MICROSPHERES (DOWCHEM
ICAL COMPANY), Expancel (Nippon Philite), Matsumoto Microsphere (Matsumoto Yushi Seiyaku), etc., and DYLITE as a polystyrene balloon.
EXPANDABLE POLYSTYRENE (A
RCO POLYMERS INC. ), EXPAND
ABLE POLYSTYRENE BEADS (BA
SF WYANDOTE CORP. ) Is used as a crosslinked styrene-acrylic acid balloon as SX863 (P).
(Japanese synthetic rubber) and the like.

Examples of the hybrid hollow body in which the surface of the organic hollow body is coated with an inert inorganic powder include Matsumoto Microsphere-MFL series (Matsumoto Yushi Seiyaku) and the like. The amounts of the hollow bodies used are the polyoxyalkylene polymers (A) and (B) and the polymer (C).
0.01 to 100 parts by weight for a total of 100 parts by weight of
Preferably 0.1 to 50 parts by weight, more preferably 0.1 to 50 parts by weight.
3 to 40 parts by weight are preferred.

When mixing a hollow body, particularly a hollow body made of a relatively brittle material such as a glass balloon, it is necessary to take care that the hollow body is not broken by the shearing force during mixing. It can be handled in the same way as a filler. (Plasticizer) As the plasticizer, a known plasticizer can be used.
The amount of the plasticizer used is preferably 0.001 to 1000 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymers (A) and (B) and the polymer (C). The following are specific examples of the plasticizer.

Phthalic esters such as di (2-ethylhexyl) phthalate, dibutyl phthalate and butylbenzyl phthalate; Dioctyl adipate, bis succinate (2-
Aliphatic carboxylic acid esters such as methylnonyl), dibutyl sebacate and butyl oleate. Alcohol esters such as pentaerythritol ester.

Phosphoric esters such as trioctyl phosphate and tricresyl phosphate. Epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxy stearate. Chlorinated paraffin. Polyester plasticizers such as polyesters obtained by reacting a dibasic acid and a dihydric alcohol.

Polymer plastics such as polyoxyalkylene, polyester, poly-α-methylstyrene, polystyrene, polybutadiene, alkyd resin, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene, and butadiene-acrylonitrile copolymer. Agent. Among these, polyoxyalkylene is preferred from the viewpoint of compatibility with the polyoxyalkylene polymers (A) and (B). As such a polyoxyalkylene, those having a molecular weight of 4000 or more are preferable,
Further, a polyoxyalkylene having an Mw / Mn of 1.5 or less, which is produced using a double metal cyanide complex or the like, is preferable because it has a low molecular weight and a low viscosity. Such a polyoxyalkylene may be a hydroxyl group-containing polyoxyalkylene or a polymer obtained by converting the hydroxyl group into another organic group. Specifically, a polymer obtained by converting a terminal hydroxyl group into a polymer sealed with a hydrocarbon group such as an alkyl group or an alkenyl group via a bond such as an ether bond, an ester bond, or a urethane bond is particularly preferable.
Most preferred is a polymer blocked with an allyl group via an ether bond.

These plasticizers can be appropriately selected according to the application and purpose. Di-phthalic acid (2-
Ethylhexyl) is most commonly used. For example, if it is desired to improve the weather resistance, a so-called high molecular weight plasticizer having a large molecular weight is used. In the case of an adhesive application, a plasticizer is not necessarily required. Rather, the adhesiveness can be improved by using a non-plastic compound that does not use a plasticizer. (Solvent) When the composition of the present invention is used as a curable composition, a solvent can be added for the purpose of adjusting the viscosity and improving the storage stability of the composition. It is useful for adjusting the viscosity in a non-plastic composition without using an agent. The use amount of the solvent is preferably 0.001 to 500 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymers (A), (B) and the polymer (C).

Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols, ketone ethers. , Ketone esters and ester ethers can be used. Alcohols are preferred because storage stability is improved when the composition of the present invention is stored for a long period of time.
As the alcohols, alkyl alcohols having 1 to 10 carbon atoms are preferable, and methanol, ethanol, isopropanol, isopentyl alcohol, hexyl alcohol and the like are particularly preferable. (Curing Acceleration Catalyst) When the curable composition of the present invention is cured, a curing acceleration catalyst for accelerating the curing reaction of the hydrolyzable group-containing silicon group may be used. Specific examples include the following compounds. One or more of them are used. The curing accelerating catalyst is a total of 100 of polyoxyalkylene polymers (A), (B) and polymer (C).
It is preferable to use 0.0001 to 10 parts by weight based on parts by weight.

Specifically, the following tin compounds can be mentioned. Tin 2-ethylhexanoate, tin naphthenate,
Various compounds of divalent tin such as tin stearate. Organic tin carboxylate such as dialkyltin dicarboxylate and dialkoxytin monocarboxylate such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate and dibutyltin maleate, dialkyltin bisacetylacetonate, dialkyltin monoacetylacetonate mono Tin chelate compounds such as alkoxides, reactants of dialkyltin oxide and ester compounds, reactants of dialkyltin oxide and alkoxysilane compounds, and various compounds of tetravalent tin such as dialkyltin dialkylsulfide.

Examples of the tin chelate compound include dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, and dibutyltin monoacetylacetonate monoalkoxide. Also,
Examples of the reaction product of the dialkyltin oxide and the ester compound include a tin compound which is made into a liquid state by heating and mixing dibutyltin oxide with a phthalic acid ester such as dioctyl phthalate or diisononyl phthalate. In this case, as the ester compound, in addition to the ester of an aliphatic or aromatic carboxylic acid, tetraethyl silicate or a partially hydrolyzed condensate thereof can be used as the ester compound.

A compound obtained by reacting or mixing these tin compounds with a low-molecular alkoxysilane or the like can also be preferably used. The following curing accelerators can be used in addition to the tin compound. Other metal salts such as alkyl titanates, organosilicon titanates, bismuth organic carboxylate, and the like.

Acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid and di-2-ethylhexyl phosphate. Aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, laurylamine, and N, N-dimethyl-octylamine; aliphatic polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; Amine compounds such as aromatic amine compounds, alkanolamines, and aminosilane coupling agents such as 3- (2-aminoethyl) amino-propyltrimethoxysilane and 3-aminopropyltrimethoxysilane.

A bismuth compound or a tin compound is preferably used in combination with an amine compound, especially a primary amine compound, because the effect of accelerating curing is improved. Further, by combining the above acidic compound and a basic compound such as an amine compound, a higher curing promoting effect is exhibited, especially at a high temperature. (Adhesiveness-imparting agent) An adhesiveness-imparting agent is used for the purpose of improving the adhesiveness with the substrate. Examples of these adhesiveness-imparting agents include silane coupling agents such as silanes containing (meth) acryloxy groups, silanes containing amino groups, silanes containing mercapto groups, silanes containing epoxy groups, and silanes containing carboxyl groups.

Examples of (meth) acryloyloxy group-containing silanes include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropylmethyldimethoxysilane. Examples of amino group-containing silanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N
-(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N- (N-vinylbenzyl-2) −
(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and the like.

The mercapto group-containing silanes include 3-silane
Examples thereof include mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Epoxy group-containing silanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like.

The carboxyl group-containing silanes include 2
-Carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (N-carboxylmethyl-2-aminoethyl) -3-aminopropyltrimethoxysilane and the like. Further, a reaction product obtained by reacting two or more silane coupling agents may be used. Examples of the reactant include a reactant of an amino group-containing silane and an epoxy group-containing silane, a reactant of an amino group-containing silane and a (meth) acryloyloxy group-containing silane, and an epoxy group-containing silane and a mercapto group. Examples of the reaction product include silane-containing reactants and mercapto group-containing silanes. These reactants are mixed with the silane coupling agent,
It is easily obtained by stirring in a temperature range of 0 ° C. for 1 to 8 hours.

The above compounds may be used alone,
More than one kind may be used in combination. The amount of the silane coupling agent used is the polyoxyalkylene polymer (A) of the present invention,
0 to 30 based on 100 parts by weight of (B) and the polymer (C)
Parts by weight are preferred. An epoxy resin may be added as an adhesion imparting agent. If necessary, an epoxy resin curing agent may be used in combination. Examples of the epoxy resin that can be added to the composition of the present invention include general epoxy resins. Specifically, the following can be exemplified. The amount used is preferably from 0 to 100 parts by weight based on 100 parts by weight of the polyoxyalkylene polymers (A), (B) and polymer (C) of the present invention.

Bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A-
Flame-retardant epoxy resin such as glycidyl ether epoxy resin, novolak epoxy resin, hydrogenated bisphenol A epoxy resin, glycidyl ether epoxy resin of bisphenol A / propylene oxide adduct,
-Diglycidyl ester epoxy resins such as glycidyl oxyglycidyl benzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various types Alicyclic epoxy resin, N, N
-Diglycidylaniline, N, N-diglycidyl-o-
Toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, hydantoin type epoxy resin, epoxy resins generally used such as epoxidized unsaturated polymer such as petroleum resin and Vinyl polymers containing epoxy groups.

Further, the epoxy resin curing agent (or curing catalyst) may be used in combination with the composition of the present invention. Examples of such a curing agent include commonly used curing agents for epoxy resins. Specifically, the following can be exemplified.
The amount used is preferably from 0.1 to 300 parts by weight based on the epoxy resin. Triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6
Amines such as tris (dimethylaminomethyl) phenol or salts thereof, or blocked amines such as ketimine compounds, polyamide resins, imidazoles,
Dicyandiamides, boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, carboxylic anhydrides such as pyromellitic anhydride, phenoxy resins,
Polyalkylene oxide polymers having at least one group capable of reacting with an epoxy group, such as carboxylic acids and alcohols, on average in the molecule (terminal aminated polyoxypropylene glycol, terminal carboxylated polyoxypropylene glycol, etc.); Hydroxyl group, carboxyl group, polybutadiene modified with an amino group, hydrogenated polybutadiene, acrylonitrile-butadiene copolymer,
Liquid terminal functional group-containing polymers such as acrylic polymers. Also, ketimine compounds can be used. (Storage stabilizer) In order to further improve the storage stability of the curable composition of the present invention, a storage stabilizer can be added. The storage stabilizer refers to a compound capable of suppressing the hydrolysis of the polyoxyalkylene polymers (A) and (B) and the polymer (C) in the presence of a small amount of water, or a compound having a high dehydration effect. Such compounds include (1) low molecular weight alcohols, (2) keto-enol tautomers, (3) mineral acids, (4) hydrolyzable alkyl esters, and (5) silicon with high reactivity with water. A compound selected from a compound, (6) a hydrolyzable organic titanium compound, (7) a silicic acid-containing compound that functions as a dehydrating agent, and (8) a mercapto group-containing compound is preferable. These can be used alone or in combination.

(1) As the low molecular weight alcohol, an alkyl monoalcohol having 10 or less carbon atoms and an alkyl polyalcohol having 10 or less carbon atoms can be used.
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2
-Butanol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 1-hexanol, octyl alcohol, 2-ethylhexanol, cellosolve, ethylene glycol, propylene glycol, glycerin and the like. Diethylene glycol, dipropylene glycol and the like can also be used.

(2) As the keto-enol tautomer, a compound having 10 or less carbon atoms can be used, and the compound is an oxygen atom-containing hydrocarbon compound having a methylene group and a carbonyl group on both sides of the methylene group in the molecule. Is preferred,
A 1,3-diketone compound having 10 or less carbon atoms or a β-ketoester compound having 10 or less carbon atoms is particularly preferred. Specific examples include acetylacetone; acetoacetate compounds such as methyl acetoacetate, ethyl acetoacetate and butyl acetoacetate; malonate compounds such as dimethyl malonate and diethyl malonate.

(3) Mineral acids include hydrochloric acid, sulfuric acid, nitric acid and the like.
No. (4) As the hydrolyzable alkyl ester, phosphoric acid
Alkyl ester, alkyl orthoformate, ortho
Alkyl acetate can be used, and specifically, [Me
_TwoCHO]_TwoP (= O) (OH), [Me_TwoCHO] P
(= O) (OH)_Two, (EtO)_TwoP (= O) (O
H), (EtO) P (= O) (OH)_Two, (MeO)_Two
P (= O) (OH), (MeO) P (= O) (O
H)_Two, (BuO) _TwoP (= O) (OH), (BuO)
P (= O) (OH)_Two, (PrO)_TwoP (= O) (O
H), (PrO) P (= O) (OH)_TwoEtc.
You. Note that Me is a methyl group, Et is an ethyl group, and Pr is
A ropyl group and Bu represent a butyl group.
It is.

Examples of the alkyl orthoformate include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate and tributyl orthoformate, and examples of the alkyl orthoacetate include trimethyl orthoacetate,
And triethyl orthoacetate. (5) Silicon compounds having high reactivity with water include polyoxyalkylene polymers (A) and (B) and silicon that hydrolyzes faster than the hydrolyzable silicon group at the terminal of polymer (C). Compounds are preferred. The rate of hydrolysis depends on the type of hydrolyzable silicon group and the number of functional groups,
In the present invention, the polyoxyalkylene polymer (B)
A silicon compound which has a high hydrolyzable rate of the hydrolyzable silicon group represented by the formula (2) at the terminal of and has higher hydrolyzability is preferred.

The following are specific examples of the silicon compound having high reactivity with water. Tetraalkyl silicates such as tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate. A partially hydrolyzed condensate of tetramethyl silicate and / or tetraethyl silicate. Alkyltrialkoxysilanes such as methyltrimethoxysilane and ethyltrimethoxysilane; Alkenyl trialkoxysilanes such as vinyltrimethoxysilane. Aryl trialkoxysilanes such as phenyltrimethoxysilane. Chlorosilanes such as methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane and diphenyldichlorosilane. Silazanes such as hexamethyldisilazane. In addition, the following compounds.

CH ₂ = Si (ON = CMe ₂ ) ₂ , Me
Si (NMe ₂ ) ₃ , MeSi (ONMe ₂ ) ₃ , Me
Si (NMeC (= O) Me) ₃ , MeSi (OCMe
= CH _{2) 3.}

(6) As a hydrolyzable organic titanium compound
Is tetraisopropoxytitanium, tetrabutoxytita
, Tetraoctyloxytitanium, and their condensation
Material, Ti (OCHMe_Two)_Two[OCMe = CHCOM
e]_Two, Ti (OBu)_Two[OC _TwoH_FourN (C_TwoH_FourO
H)_Two]_Two, Ti (OH)_Two[OCHMeCOO
H]_Two, Ti (OCHMe_Two)_Three[OCOC₁₇H₃₅],
Ti (OCHMe_Two) [OCOC ₁₇H₃₅]_Three, Isopro
Poxytitanium dimethacrylate monoisostearate,
Isopropoxy titanium tris (4-aminobenzoate
G), isopropoxy titanium tris (dioctylphosph
And the like.

(7) As the silicic acid-containing compound functioning as a dehydrating agent, zeolite is preferable. (8) Mercapto group-containing compounds include alkyl mercaptans such as dodecyl mercaptan and t-butyl mercaptan, mercapto silanes such as γ-mercapto propyl trimethoxy silane, 2-mercapto propionic acid,
Mercapto group-containing carboxylic acids such as thiosalicylic acid; mercapto group-containing ester compounds such as 2-ethylhexyl thioglycolate; Preferred are compounds selected from polymers, thiophenols, thiobenzoic acids and the like.

Among them, (1) low molecular weight alcohol, (2) keto-enol tautomer, (3) mineral acid, (4) hydrolyzable alkyl ester, (5) high reactivity with water. Compounds selected from silicon compounds and (8) mercapto group-containing compounds are particularly preferred, and (5)
A silicon compound having high reactivity with water is most preferable, and a partially hydrolyzed condensate of vinyltrimethoxysilane, tetraethoxysilane, tetramethylsilicate and / or tetraethylsilicate is most preferable in terms of cost and effect.

The content of the storage stabilizer was 10% in total for the polyoxyalkylene polymers (A), (B) and (C).
0 to 30 parts by weight relative to 0 parts by weight is preferred. Compounds that generate strong acids by hydrolysis, such as mineral acids or chlorosilanes, exert their effects at 1 part by weight or less.
These storage stabilizers are preferably added before or at least simultaneously with the addition of the curing catalyst. (Thixotropic agent) A thixotropic agent may be used to improve sagging. As such a thixotropic agent, hydrogenated castor oil, fatty acid amide and the like are used. (Antiaging Agent) Examples of the antiaging agent include hindered amines, benzotriazoles, benzophenones,
Commonly used antioxidants, light stabilizers, and ultraviolet absorbers such as benzoate-based, cyanoacrylate-based, acrylate-based, hindered phenol-based, phosphorus-based, and sulfur-based compounds are appropriately used. These anti-aging agents are
They may be used in combination, and it is particularly preferable to use them in combination. The amount of the antioxidant used is a polyoxyalkylene polymer (A),
0 based on a total of 100 parts by weight of (B) and the polymer (C).
It is preferably in the range of 10 to 10 parts by weight.

The antioxidant is preferably a hindered phenol-based and / or phosphite-based antioxidant, and specific examples thereof include the following. Nocrack 200,
Nocrack M-17, Nocrack SP, Nocrack SP
-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS
-7, Nocrack DAH (all manufactured by Ouchi Shinko Chemical Co., Ltd.), ADK STAB AO-30, ADK STAB AO-
40, Adekastab AO-50, Adekastab AO-6
0, ADK STAB AO-616, ADK STAB AO-1
5, ADK STAB AO-18, ADK STAB 328, ADK STAB AO-37 (all manufactured by Asahi Denka Kogyo Co., Ltd.), IRGANOX-245, IRGANOX-2
59, IRGANOX-565, IRGANOX-10
10, IRGANOX-1035, IRGANOX-1
076, IRGANOX-1081, IRGANOX-
1098, IRGANOX-1222, IRGANOX
-1330 and IRGANOX-1425WL (both manufactured by Ciba Specialty Chemicals Co., Ltd.).

As the light stabilizer, a secondary and / or tertiary hindered amine compound is preferable. Specifically, tinuvin 622LD, tinuvin 144, CHIMAASSOR
B944LD, CHIMASSORB119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-57, ADK STAB LA-6
2, ADK STAB LA-67, ADK STAB LA-63
P, ADK STAB LA-68LD, ADK STAB LA-
601 (all manufactured by Asahi Denka Kogyo KK), SANOL LS-770, SANOL LS-765, SANOL LS
-292, SANOL LS-2626, SANOL LS-1
114 and Sanol LS-744 (both manufactured by Sankyo Co., Ltd.).

As the ultraviolet absorber, a benzotriazole compound or a benzoate compound is preferable. Specifically, tinuvin P, tinuvin 234, tinuvin 32
0, Tinuvin 326, Tinuvin 327, Tinuvin 32
9, Tinuvin 213 and Tinuvin 120 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.).

Further, a mixture of the above compounds, such as Tinuvin B5353 and Tinuvin B75 (both manufactured by Ciba Specialty Chemicals Co., Ltd.), can also be used. (Air-Curable Compound, Photocurable Compound) An air oxidation-curable compound or a photocurable compound can be added for the purpose of improving the adhesion and surface tack of a paint over a long period of time. These compounds may be used alone, but are more preferably used in combination. The amount used is preferably 0.001 to 50 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymers (A) and (B) and the polymer (C).

As the air oxidation-curable compound, a compound containing an unsaturated group which is polymerized by oxygen in the air is preferably used. Specifically, drying oils such as paulownia oil, linseed oil, eno oil, soybean oil, sunflower oil, hemp oil, etc., various alkyd resins obtained by denaturing the drying oils, reaction products of drying oils and functional polyoxyalkylenes Product, reaction product of a drying oil and an isocyanate compound (urethane oil), acrylic polymer modified by a drying oil, epoxy resin modified by a drying oil, silicone resin modified by a drying oil, and polybutadiene , Diene polymers such as diene polymers and copolymers having 5 to 8 carbon atoms, and allyloxy group-containing polyester compounds obtained by polycondensation of allyloxy group-containing glycol and polyvalent carboxylic acid (air-drying unsaturated polyester) And various modified products of the polymer and copolymer (maleization-modified, boiled oil-modified, etc.).

As the photocurable compound, a compound which undergoes a chemical change in the molecular structure in a very short time due to the action of light to cause a physical change such as curing can be used. Many compounds of this type are known, such as monomers, oligomers, resins, and compositions containing them, and are commercially available, and any of these known compounds can be used. Of these, polyfunctional acrylates are most commonly used. (Modulus modifier) A compound capable of forming a compound having one silanol group in the molecule or a compound having one silanol group in the molecule for the purpose of adjusting the modulus of the cured product and the surface tackiness. Can be added. The addition of these compounds has the effect of reducing the modulus without deteriorating the tackiness of the surface. The amount used is 0 based on the total of 100 parts by weight of the polyoxyalkylene polymers (A) and (B) and the polymer (C).
-10 parts by weight is preferred.

Examples of the compound having one silanol group in the molecule include trimethylsilanol, triethylsilanol, triphenylsilanol and the like. Compounds capable of forming a compound having one silanol group in the molecule include N-trimethylsilylacetamide, hexamethyldisilazane, methoxytrimethylsilane, ethoxytrimethylsilane, isopropyloxytrimethylsilane, butoxytrimethylsilane, hexyloxytrimethylsilane , 2-ethylhexyloxysilane,
n-octyloxysilane, 2-chloropropyloxytrimethylsilane, phenoxytrimethylsilane, 2-
Examples include methylphenoxytrimethylsilane, 2-chlorophenoxytrimethylsilane, methoxydimethylphenylsilane, methoxymethyldiphenylsilane, and phenoxydimethylphenylsilane. Also, ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol And the like, in which the hydroxyl group of a polyvalent hydroxy compound such as the above is converted into a trimethylsilyl ether. (Others) As pigments, inorganic pigments such as iron oxide, chromium oxide and titanium oxide and organic pigments such as phthalocyanine blue and phthalocyanine green can be used.

Known additives such as a fungicide, a flame retardant and the like can be used depending on the application. The room temperature curable composition of the present invention can be used for sealants, waterproofing materials, adhesives, coating agents, etc., and is particularly used for applications requiring sufficient cohesion of the cured product itself and dynamic followability to adherends. It is suitable.

[0110]

EXAMPLES Examples and comparative examples of the present invention will be described below. In these examples, “parts” means “parts by weight”. In (Production Example 1-1) to (Production Example 1-6), 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. Mw / Mn is a value measured by gel permeation chromatography using tetrahydrofuran as a solvent. The calibration curve was prepared using a standard sample of styrene. (Production Example 1-1) A polymer having a hydroxyl value-converted molecular weight of 17000 and Mw / Mn = 1.3 obtained by reacting propylene oxide with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. A methanol solution of sodium methoxide was added to oxypropylene triol, 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 to remove unreacted allyl chloride and purified to obtain a polypropylene oxide (U1) having an allyl group at the terminal. The polymer U1 is reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to form a polypropylene oxide (P) having a methyldimethoxysilyl group at a terminal.
1) was obtained. (Production Example 1-2) Using propylene glycol as an initiator,
A method similar to that of Production Example 1 using a polyoxypropylene diol having a hydroxyl value-converted molecular weight of 17000 and Mw / Mn = 1.3 obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Thus, polypropylene oxide having an allyl group at the end was obtained. This reaction product was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polypropylene oxide (P2) having a methyldimethoxysilyl group at a terminal. (Production Example 1-3) A methanol solution of sodium methoxide was added to polyoxypropylene diol having a hydroxyl value-converted molecular weight of 3,000 obtained using a potassium hydroxide catalyst, and methanol was distilled off under reduced pressure while heating. The hydroxyl group was converted to a sodium alkoxide. Next, after reacting with chlorobromomethane to increase the molecular weight, subsequently, allyl chloride was reacted to obtain a polypropylene oxide having an allyloxy group at the terminal (Mw / Mn = 2.0). This was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polypropylene oxide (P3) having a methyldimethoxysilyl group at a terminal and a molecular weight of 9000. (Production Example 1-4) A polystyrene having a hydroxyl value-converted molecular weight of 17000 and Mw / Mn = 1.3 obtained by reacting propylene oxide with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Using oxypropylene triol, a polypropylene oxide having an terminal allyl group was obtained in the same manner as in Production Example 1.
To this reaction product, a silyl compound, 3-mercaptopropyltrimethoxysilane, was added to a polymerization initiator, 2,2
The reaction was carried out using 2'-azobis (2-methylbutyronitrile) to obtain a polypropylene oxide (P4) having a trimethoxysilyl group at a terminal. (Production Example 1-5) Using propylene glycol as an initiator,
A method similar to that of Production Example 1 using a polyoxypropylene diol having a hydroxyl value-converted molecular weight of 17000 and Mw / Mn = 1.3 obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Thus, polypropylene oxide having an allyl group at the end was obtained. To this reaction product, a silyl compound, 3-mercaptopropyltrimethoxysilane, and a polymerization initiator, 2,2′-azobis (2-methylbutyronitrile)
To obtain a polypropylene oxide (P5) having a trimethoxysilyl group at the end. (Production Example 1-6) Propylene oxide was polymerized using glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst, to give a hydroxyl value-converted molecular weight of 10
000 and Mw / Mn = 1.2 polyoxypropylene triol was obtained and purified. To this was added γ-isocyanatopropyltrimethoxysilane, and a urethanization reaction was performed to obtain a polypropylene oxide (P6) having a trimethoxysilyl group at a terminal. (Production Example 2-1) Polypropylene oxide (P1) 15
g was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., the polymerizable monomers shown in Table 1 were mixed to a total of 40 g in a weight ratio shown in the table. A mixture of a solution of 0.8 g of azobisisobutyronitrile and 45 g of polypropylene oxide (P4) was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed under reduced pressure at 100 ° C. to obtain a polymer composition Pa of the present invention. (Production Example 2-2) Polypropylene oxide (P4) 30
g was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., the polymerizable monomers shown in Table 1 were mixed to a total of 40 g in a weight ratio shown in the table. A mixture of a solution in which 0.8 g of azobisisobutyronitrile was dissolved and 30 g of polypropylene oxide (P1) was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed at 100 ° C. under reduced pressure to obtain a polymer composition Pb of the present invention. (Production Example 2-3) Polypropylene oxide (P4) 15
g was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., the polymerizable monomers shown in Table 1 were mixed to a total of 40 g in a weight ratio shown in the table. A mixture of a solution in which 0.8 g of azobisisobutyronitrile was dissolved and 45 g of polypropylene oxide (P1) was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed under reduced pressure at 100 ° C. to obtain a polymer composition Pc of the present invention. (Production Example 2-4) Polypropylene oxide (P1) 60
g was placed in a reactor equipped with a stirrer, and diluted by adding 120 g of toluene, and the mixture was uniformly mixed while heating to 100 ° C. This was mixed with the polymerizable monomers shown in Table 1 in a weight ratio shown in the table so that the total amount became 40 g.
A solution in which 0.4 g of 2'-azobisisobutyronitrile was dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After the dropwise addition, a toluene solution of 0.3 g of 2,2'-azobisisobutyronitrile was further added dropwise over 30 minutes, and the mixture was heated and stirred at the same temperature for 3 hours. Polypropylene oxide (P4) 150 was added to a toluene solution of the obtained copolymer.
g, and the mixture was stirred and mixed for 30 minutes, and then toluene was distilled off under reduced pressure at 100 ° C. to obtain a polymer composition Pd of the present invention. (Production Example 2-5) Polypropylene oxide (P5) 60
30 g of the resulting mixture was placed in a reactor equipped with a stirrer.
While keeping the polymerizable monomers shown in Table 1 in a total weight of 40 g at the weight ratio shown in the table, further dissolving 0.8 g of 2,2'-azobisisobutyronitrile. Solution and remaining 30 of polypropylene oxide (P5)
The mixture was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed at 100 ° C. under reduced pressure. Polypropylene oxide (P
2) 150 g was added, and the mixture was stirred and mixed for 1 hour to obtain a polymer composition Pe of the present invention. (Production Example 2-6) Polypropylene oxide (P1) 30
g was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., the polymerizable monomers shown in Table 1 were mixed to a total of 40 g in a weight ratio shown in the table. A mixture of a solution of 0.8 g of azobisisobutyronitrile and 30 g of polypropylene oxide (P4) was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed at 100 ° C. under reduced pressure. 150 g of polypropylene oxide (P4) was added to the obtained copolymer, and 1
After stirring and mixing for an hour, a polymer composition Pf of the present invention was obtained. (Production Example 2-7) Polypropylene oxide (P1) 60
g was placed in a reactor equipped with a stirrer, and diluted by adding 120 g of toluene, and the mixture was uniformly mixed while heating to 100 ° C. This was mixed with the polymerizable monomers shown in Table 1 in a weight ratio shown in the table so that the total amount became 40 g.
A solution in which 0.4 g of 2'-azobisisobutyronitrile was dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After the dropwise addition, a toluene solution of 0.3 g of 2,2'-azobisisobutyronitrile was further added dropwise over 30 minutes, and the mixture was heated and stirred at the same temperature for 3 hours. 75 g of polypropylene oxide (P1) was added to a toluene solution of the obtained copolymer.
And 75 g of polypropylene oxide (P4), and 3
After stirring and mixing for 0 minutes, toluene was distilled off under reduced pressure at 100 ° C. to obtain a polymer composition Pg of the present invention. (Production Example 2-8) 60 g of a polypropylene oxide (U1) having an allyl group at the end was placed in a reactor equipped with a stirrer, and 120 g of toluene was added to dilute the mixture.
The mixture was uniformly mixed while being heated to 00 ° C. This was mixed with the polymerizable monomers shown in Table 1 in a total weight of 40 g at the weight ratio shown in the table, and a solution in which 0.4 g of 2,2'-azobisisobutyronitrile was further dissolved was added to a nitrogen atmosphere. The solution was added dropwise over 3 hours while stirring under the solution. After dropping,
After a toluene solution of 0.3 g of 2′-azobisisobutyronitrile was added dropwise over 30 minutes, the mixture was heated and stirred at the same temperature for 3 hours. 75 g of polypropylene oxide (P1) and 75 g of polypropylene oxide (P4) were added to a toluene solution of the obtained copolymer, and the mixture was stirred and mixed for 30 minutes.
The toluene was distilled off under reduced pressure at 00 ° C. to obtain a polymer composition Ph of the present invention. (Production Example 2-9) 50 g of xylene in a reactor equipped with a stirrer
And keeping the temperature at 110 ° C., mixing with the polymerizable monomer shown in Table 1 in a total weight of 120 g at the weight ratio shown in the table, and further 3 g of 2,2′-azobisisobutyronitrile. While stirring the solution in which
It was dropped over time. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 2 hours. 75 g of polypropylene oxide (P3) and 75 g of polypropylene oxide (P4) were added to the xylene solution of the obtained copolymer, and after stirring and mixing for 30 minutes,
Xylene was distilled off under reduced pressure at 100 ° C. to obtain a polymer composition Pi of the present invention. (Production Example 2-10) Xylene 50 was added to a reactor equipped with a stirrer.
g, while maintaining the temperature at 110 ° C., mixing the polymerizable monomers shown in Table 1 in a total weight of 120 g at the weight ratio shown in the table, and further adding 2,2′-azobisisobutyronitrile. A solution in which 3 g was dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 2 hours. 75 g of polypropylene oxide (P1) and 75 g of polypropylene oxide (P4) are added to the obtained xylene solution of the copolymer, and the mixture is stirred and mixed for 30 minutes. The product Pj was obtained. (Production Example 2-11) Polypropylene oxide (P4) 6
30 g of the 0 g were placed in a reactor equipped with a stirrer,
While maintaining the temperature at 0 ° C., the polymerizable monomers shown in Table 1 were mixed at a weight ratio shown in the table so as to be 40 g in total, and 0.8 g of 2,2′-azobisisobutyronitrile was further dissolved therein. Solution and the remaining 30 of polypropylene oxide (P4)
The mixture was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, unreacted monomers were removed under reduced pressure at 100 ° C. to obtain a polymer composition Pk as a comparative example. (Production Example 2-12) Xylene 50 was added to a reactor equipped with a stirrer.
g, while maintaining the temperature at 110 ° C., mixing the polymerizable monomers shown in Table 1 in a total weight of 120 g at the weight ratio shown in the table, and further adding 2,2′-azobisisobutyronitrile. A solution in which 3 g was dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 2 hours. 75 g of polypropylene oxide (P3) and 75 g of polypropylene oxide (P6) were added to the obtained xylene solution of the copolymer, and the mixture was stirred and mixed for 30 minutes. Then, xylene was distilled off under reduced pressure at 100 ° C. to obtain a polymer as a comparative example. The composition Pm was obtained. (Production Example 2-13) Xylene 50 was added to a reactor equipped with a stirrer.
g, while maintaining the temperature at 110 ° C., mixing the polymerizable monomers shown in Table 1 in a total weight of 120 g at the weight ratio shown in the table, and further adding 2,2′-azobisisobutyronitrile. A solution in which 3 g was dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 2 hours. 150 g of polypropylene oxide (P1) was added to the xylene solution of the obtained copolymer, and the mixture was stirred and mixed for 30 minutes, and then xylene was distilled off under reduced pressure at 100 ° C. to obtain a polymer composition Pn as a comparative example. (Production Example 2-14) A weight ratio of polypropylene oxide (P1) to polypropylene oxide (P4) of 50: 5.
0, and as a comparative example, the polymer composition P
q was obtained. Table 1 shows the monomers and the like used in each Production Example and their weight ratios.

[0111]

[Table 1]

(Production Example 3-1) Polymer Plasticizer A glycerol-initiated initiator was used to react propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Using polyoxypropylene triol with Mn = 1.3, a polypropylene oxide (L1) having an allyl group at the end was obtained in the same manner as in Production Example 1. (Production Example 3-2) Polymer plasticizer Polymerization of propylene oxide was carried out using dipropylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst, to give a hydroxyl value-converted molecular weight of 800.
After obtaining polyoxypropylene diol having 0 and Mw / Mn = 1.2, it was purified. (L2) (Production Example 4-1) Curing acceleration catalyst In a glass reactor, 0.2 mol of dibutyltin oxide was added to 150 cm ³ of toluene, and 0.1 mol of 2-ethylhexanol was added. The reaction was continued while removing the azeotropic water until the theoretical amount of water had been distilled off. After that, 0.1 mol of acetylacetone was added, and while removing water azeotropically with toluene,
The reaction was continued until the theoretical amount of water had been distilled off. Filtration was performed to remove a trace amount of precipitate, and toluene was distilled off under reduced pressure to obtain a pale yellow tin compound (M1). (Production Example 4-2) Curing Acceleration Catalyst To a glass three-necked flask equipped with a reflux condenser and a stirrer, 1 mol of dibutyltin oxide and 0.5 mol of ethyl 2-ethylhexanoate were added, and the mixture was stirred under a nitrogen atmosphere. Heating at 120 ° C. for 5 hours gave a uniform pale yellow tin compound (M2). (Production Example 5-1) Modulus Modifier In a glass reaction vessel equipped with a dropping funnel, a reflux condenser, and a stirrer, 1 mol of trimethylolpropane was added, and 3.3 mol of ground sodium hydroxide was further added. . 2. Trimethylchlorosilane from the dropping funnel at room temperature with stirring.
0 mol was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the mixture was stirred for 8 hours. As the reaction progressed, fine sodium chloride was precipitated in the reaction vessel. By analyzing the trimethylsilyl group in the nuclear magnetic resonance spectrum,
After confirming that the reaction was almost completed, the reaction mixture was filtered, and the filtrate was washed thoroughly with an aqueous ammonium chloride solution and ion-exchanged water until the aqueous layer was almost pH 7 by checking with a pH test paper, and then saturated sodium chloride was added. After washing with aqueous solution,
The organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was removed by filtration and purified by distillation under reduced pressure to obtain trimethylsilyl ether of trimethylolpropane (N1). (Production Example 5-2) Modulus Modifier In a glass reaction vessel equipped with a dropping funnel, a reflux condenser, and a stirrer, 1.5 mol of 2-ethylhexyl alcohol was placed, and 0.5 mol of trimethylchlorosilane and hexamethanol were added at room temperature. A mixture of 0.5 mol of methyldisilazane was added dropwise with stirring over 2 hours. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 5 hours, further added with 0.2 mol of methanol, and allowed to stand at room temperature overnight. The next day, ammonium chloride by-produced was removed by filtration, and the filtrate was washed with an aqueous ammonium chloride solution, dried over anhydrous sodium sulfate, filtered, and purified by distillation under reduced pressure to obtain trimethylsilyl ether of 2-ethylhexyl alcohol (N2 ) Got. (Test Example 1) 90 g of each of the polymer compositions Pa to Pj of the present invention and the comparative polymer compositions Pk, Pm, Pn, and Pq
Into a 100 ml glass bottle,
The viscosity at 5 ° C. was measured. Table 2 shows the measurement results of the viscosity and the handleability of the polymer (especially easy to handle, easy to handle: good, and difficult to handle: poor).

[0113]

[Table 2]

(Test Example 2) The polymer compositions Pa to
Pj, and comparative polymer compositions Pk, Pm, Pn, Pq
For 100 parts of each polymer composition, a modulus modifier,
After adding and mixing an air-curable compound and a thixotropy-imparting agent, further adding a filler, a plasticizer, an adhesion-imparting agent, a photocurable compound, and an antioxidant, and uniformly mixing the mixture with the main agent. did. On the other hand, a curing catalyst in which 2-ethylhexanetin and laurylamine were mixed and reacted at a weight ratio of 3: 1, a plasticizer, and a filler were mixed, and this was used as a curing agent. The type and amount of each additive are as shown in Table 3.

The composition obtained by mixing the above main agent and the curing agent was mixed at 23 ° C. and 50% humidity at a width of 25 m.
m, length 100mm, thickness 3mm aluminum plate,
Coating is performed so as to have an adhesion area of 25 mm × 25 mm and a thickness of about 0.2 mm. After 30 seconds, another aluminum plate is alternately overlapped and adhered. Tensile shear bond strength (unit: kg / cm ² ) was measured at the speed.

An H-shaped test piece was prepared from the same composition according to JIS A5758 using an aluminum plate as the adherend. After curing for 14 days in a standard state and further for 14 days at 30 ° C., a tensile test was performed to measure the maximum elongation (unit:%). Table 3 shows the results.

[0117]

[Table 3]

(Test Example 3) Polymer compositions Pa to of the present invention
Pj, and comparative polymer compositions Pk, Pm, Pn, Pq
For 100 parts of each polymer composition, an antioxidant and a thixotropic agent were mixed and dispersed, and a filler from which water was removed by heating and drying was added and mixed, and a plasticizer and a storage stabilizer were further added. Added and mixed. Further adhesion imparting agent,
After the curing catalyst was added and mixed and defoamed, the composition was filled into a sealing material cartridge capable of blocking the entry of moisture in the air to obtain a composition. Table 4 shows the type and amount of each additive.
As shown in FIG.

The obtained composition was extruded from a cartridge, applied to a 1 mm thick aluminum plate to a thickness of 5 mm, and cured at 20 ° C. under a humidity of 65% for 7 days. Exposure test was conducted using a company-made Sunshine Super Long Life Weather Meter, and 500
The surface state after 1000 hours and 1000 hours was observed. Table 4 shows the results. In addition, the evaluation of the weather resistance was as follows: ：: no crack was observed, ×: crack was observed.

[0120]

[Table 4]

(Test Example 4) Polymer compositions Pa to of the present invention
Pj, and comparative polymer compositions Pk, Pm, Pn, Pq
To 100 parts of each polymer composition, an antioxidant and a thixotropy-imparting agent were mixed and dispersed, and a filler and a pigment from which water had been removed in advance by heating and drying were added and mixed. Was added and mixed. Further, an adhesiveness-imparting agent and a curing catalyst were added thereto, followed by mixing and defoaming, followed by filling in a sealing material cartridge capable of blocking entry of moisture in the air to obtain a composition. The type and amount of each additive are as shown in Table 5.

The obtained composition was extruded from the cartridge, poured into a cylindrical (4 cm diameter) cup so as to have a thickness of 4 cm, and left in an atmosphere of 20 ° C. and 65% humidity for 6 hours. Then, using a penetrometer conforming to JIS K2530, using a 1.25 g needle for asphalt, the state of hardening from the surface to the depth direction was measured by inserting the needle for 5 seconds from top to bottom in the vertical direction. It was measured as a degree (unit: cm). Higher penetration indicates that hardening from the surface has not progressed. Table 5 shows the results.

[0123]

[Table 5]

From the results shown in Table 2, handling of a composition using a polymer as the component (B) of the present invention obtained from 3-mercaptopropyltrimethoxysilane as a polypropylene oxide having a trimethoxysilyl group at a terminal is shown. It can be seen that the composition using a polymer other than the component (B) obtained from γ-isocyanatopropyltrimethoxysilane is difficult to handle while having good properties.

Further, from the results in Table 3, it can be seen that the adhesive strength is improved by containing the component (C) of the present invention. Further, from the results in Table 4, it is found that the weather resistance is improved by containing the component (C) of the present invention. This is particularly remarkable when a component obtained by polymerization of a polymerizable monomer containing an alkyl acrylate or an alkyl methacrylate (component (H) of the present invention) is used as the component (C). .

Further, from the results in Table 3, it can be seen that the elongation characteristics of the cured product are improved by containing the component (A) of the present invention. It can be seen that the inclusion speed significantly increases the curing speed. By adjusting the proportions of the components (A) and (B), it is possible to freely adjust the curing characteristics and the elongation characteristics of the cured product (Examples Pa to Pc).

[0127]

As described above, according to the present invention,
Using a polymer having a hydrolyzable silicon group obtained using a silane compound that can be easily handled industrially as a raw material,
It is possible to obtain a curable composition having low viscosity and excellent handleability, and excellent cured physical properties after curing such as adhesiveness and mechanical strength and weather resistance, and furthermore, a curing speed which can be adjusted in a wide range. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H017 AA03 AB15 AB17 AC01 AC05 AC19 4J002 AA01X CH05W 4J005 AA02 BB02 BB04 BD08

Claims (7)

[Claims] 1. After introducing an unsaturated group into the terminal of a polyoxyalkylene polymer (A) having a hydrolyzable silicon group represented by the following formula (1) and a polyoxyalkylene polymer having a hydroxyl group: A polyoxyalkylene polymer (B) having a hydrolyzable silicon group represented by the following formula (2) obtained by reacting the unsaturated group with a mercapto group of a silicon compound represented by the formula (3): ),as well as,
A room temperature curable composition (D) containing a polymer (C) obtained by polymerizing a polymerizable unsaturated group-containing monomer (E). —SiX ₂ R ¹ (1) (in the formula (1), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, X may be the same or different.) —SiX ₃ (2) (In the formula (2), X is the same as above. Three Xs may be the same or different.) HS-R ^2- SiX ₃ (3) (In the formula (3), X is the same as above. Three Xs may be the same or different. R ² is a divalent hydrocarbon group having 1 to 17 carbon atoms.) ) 2. The polymer (C) is a polymerizable unsaturated group-containing monomer (E) in the polyoxyalkylene polymer (A) and / or the polyoxyalkylene polymer (B).
The room temperature-curable composition (D) according to claim 1, which is a polymer (C) obtained by polymerizing the composition. 3. The polymer (C) is a polymerizable unsaturated group-containing monomer in the polyoxyalkylene polymer (A) and / or the precursor (F) of the polyoxyalkylene polymer (B). The room temperature curable composition (D) according to claim 1, which is a polymer (C) obtained by polymerizing the polymer (E). 4. A polymer (C) is obtained by polymerizing a polymerizable unsaturated group-containing monomer (E) in a solvent and / or a diluent, and then the polyoxyalkylene polymer (A) and The room-temperature-curable composition (D) according to any one of claims 1 to 3, which is obtained by removing part or all of a solvent and / or a diluent after mixing with the polyoxyalkylene polymer (B). 5. The polyoxyalkylene polymer (A)
The room temperature curable composition (D) according to claim 1, wherein the molecular weight of the polyoxyalkylene polymer (B) is 8,000 to 50,000. 6. The polyoxyalkylene polymer (A)
And / or the molecular weight distribution Mw / Mn of the polyoxyalkylene polymer (B) is 1.7 or less.
The room temperature curable composition (D) described. 7. The polyoxyalkylene polymer (A)
And / or the polyoxyalkylene polymer (B) is
The room temperature curable composition (D) according to any one of claims 1 to 6, which is a derivative of a polyoxyalkylene polymer obtained by polymerizing a cyclic ether using a double metal cyanide complex as a catalyst in the presence of an initiator.