JP3491564B2 - Method for producing polymer, curable composition using polymer obtained by the method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer having a low viscosity, excellent handleability and storage stability, and a curable and cured product which is cured in the presence of moisture containing the polymer. The present invention relates to a curable composition having excellent mechanical properties and weather resistance.

[0002]

2. Description of the Related Art The method of using a polymer containing a hydrolyzable silicon group in a curable composition has been well known so far. Among them, a polyoxyalkylene-based polymer containing a hydrolyzable silicon group is used. The coalesced product has a low viscosity at room temperature, is extremely flexible in the physical properties of a cured product, and is excellent in elongation properties and the like, and thus is used for sealing materials, adhesives, and the like.

However, such a polyoxyalkylene polymer has insufficient weather resistance and adhesive strength to various substrates.

In order to solve these problems, for example, JP-A-59-122541 and JP-A-60-3.
In Japanese Patent No. 1556 and Japanese Patent Laid-Open No. 1311271,
A polyoxyalkylene polymer having a hydrolyzable silicon group is mixed with a polymer obtained by polymerizing a polymerizable monomer such as an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester having a hydrolyzable silicon group. Thus, a method of improving weather resistance is disclosed.

However, since the acrylic acid ester-based polymer generally has a higher cohesive force than the polyoxyalkylene polymer, the viscosity of the mixture tends to increase, which is a big problem in practical use. It was Therefore, in order to maintain a practical viscosity in the above method, the polyoxyalkylene polymer itself must include a large amount of a polymer having a relatively low molecular weight, especially in terms of curability and elongation at break. It was not enough.

Further, in Japanese Patent Application Laid-Open No. 6-172631, a polyoxyalkylene polymer having a hydrolyzable silicon group and having a narrow molecular weight distribution, and an alkyl acrylate and / or methacrylic acid alkyl ester having a hydrolyzable silicon group are disclosed. It discloses a method of mixing and using a polymer obtained by polymerizing a polymerizable monomer such as.

In this method, since a practical viscosity level can be realized without particularly containing a low molecular weight polymer, the curability in the deep part and the strength of the resin itself can be improved as compared with the above-mentioned methods. Can be improved. However, it was still insufficient for use in applications requiring higher strength.

Further, by mixing the polyoxyalkylene polymer with a polymer obtained by polymerizing a polymerizable monomer such as an alkyl acrylate and / or an alkyl methacrylate having a hydrolyzable silicon group. The method for obtaining the desired composition was not always satisfactory in storage stability, such as causing phase separation depending on storage conditions.

Furthermore, as another method, Japanese Patent Laid-Open No. 59-7 is available.
In 8223, a polymerizable monomer such as an alkyl acrylate and / or an alkyl methacrylate having a hydrolyzable silicon group is polymerized in the presence of a polyoxyalkylene polymer having a hydrolyzable silicon group. The resulting polymer, or the radical polymerization having a hydrolyzable silicon group in the presence of a polyoxyalkylene polymer having a hydrolyzable silicon group in JP-A-60-228516 and JP-A-60-228517. A polymer obtained by polymerizing a special polymerizable unsaturated group-containing monomer using an initiator and / or a radical chain transfer agent is disclosed. However, even in these methods, a practical viscosity can be obtained. In order to retain it, the polyoxyalkylene polymer must also contain a large amount of relatively low molecular weight polymer, and the breaking strength of the material must be increased. Although good is found, it was still insufficient in terms of curability and elongation at break.

Then, Japanese Patent Laid-Open No. 5-194 by the present applicant
In 677 and JP-A-7-62219, a glycidyl group-containing monomer is essential, and a vinyl monomer is added in the presence of a polyoxyalkylene polymer having a hydrolyzable silicon group and a narrow molecular weight distribution. Polymers obtained by polymerization are disclosed.

[0011]

In view of the above problems, one of the objects of the present invention is to provide a polymer having a low viscosity and being excellent in handleability and storage stability. Also another 1
One object is to provide a curable composition containing the above polymer, which is excellent in curability, mechanical properties of a cured product, and weather resistance.

[0012]

In order to achieve the above object, the present inventors have studied a method of polymerizing a vinyl monomer in the presence of a hydrolyzable silicon group-containing polyoxyalkylene polymer. As a result, polymerization containing at least one monomer selected from alkyl acrylate and alkyl methacrylate monomers in the presence of a polyoxyalkylene polymer having a moderately unsaturated group and a narrow molecular weight distribution. It was found that a polymer having a low viscosity and excellent handleability and storage stability can be obtained by polymerizing a volatile monomer. Furthermore, they have found that the curability of the curable composition, the mechanical properties of the cured product, and the weather resistance are improved by incorporating the polymer into the curable composition, and the present invention has been completed.

That is, the first aspect of the present invention has the following features 1) to 3) in which a cyclic ether is polymerized in the presence of an initiator using a complex metal cyanide complex as a catalyst.
A hydrolyzable silicon group represented by the following general formula (1) is added to
After obtaining a polyoxyalkylene polymer (A) containing 01 mmol / g or more, the polyoxyalkylene polymer (A) and an acrylic acid alkyl ester or methacrylic acid alkyl ester monomer as a polymerizable monomer are selected. At least one type of monomer (B), or the above-mentioned monomer (B) and another polymerizable unsaturated group-containing monomer (C) are polymerized. The present invention provides a method for producing a coalesced product (G).

1) The molecular weight distribution Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.
7 or less 2) Molecular weight of 8,000 to 50,000 3) 0.01 m of unsaturated group at the terminal and / or side chain of the main chain
mol / g or more containing the general ^{_{formula: -SiX a R 1 3-a}} ... (1) (R 1: 1 monovalent organic substituted or unsubstituted 1 to 20 carbon atoms
Group, X: hydroxyl group or hydrolyzable group, a: an integer of 1 to 3.
However, when a plurality of R ¹ 's are present, those R ^1's are
It may be the same or different. If there are multiple Xs,
However, those X may be the same or different. )

As the monomer (B), at least one monomer (D) selected from an alkyl acrylate and an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, It is preferable to use in combination with at least one monomer (E) selected from alkyl acrylate and alkyl methacrylate having an alkyl group having 10 or more carbon atoms.

[0016]

[0017]

The other polymerizable unsaturated group-containing monomer (C) is essential as the polymerizable monomer, and the other polymerizable unsaturated group-containing monomer (C) is It preferably contains a hydrolyzable silicon group represented by the general formula (1).

Next, a second aspect of the present invention is based on the above manufacturing method.
A curable composition (hereinafter referred to as curable composition (H)) containing the polymer (G) thus obtained and a curing accelerating catalyst is provided.

In the second aspect of the present invention, the curable composition (H) comprises the polymer (G) and the main chain at the terminal and / or side chain thereof is hydrolyzed by the general formula (1). It is preferable to contain a polyoxyalkylene polymer (F) containing 0.1 mmol / g or more of a crystalline silicon group.

The polyoxyalkylene polymer (F) preferably has the following characteristics 1) and 2).

1) The molecular weight distribution Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.7 or less. 2) The molecular weight is 8,000 to 50,000. The combination (F) is preferably a derivative of a polymer obtained by polymerizing a cyclic ether in the presence of an initiator using a complex metal cyanide complex as a catalyst.

In the present invention, the polymer (G) is obtained by polymerizing the above polymerizable monomer in the presence of the polyoxyalkylene polymer (A) containing an unsaturated group in an amount of 0.01 mmol / g or more, The polyoxyalkylene polymer (A)
Is presumed to be incorporated in a form grafted to the polymer.

As a result, the polyoxyalkylene polymer (A) does not separate from the polymer of the polymerizable monomer, and the end of the main chain and / or the main chain having the same structure as the polyoxyalkylene polymer (A) Alternatively, even when a polyoxyalkylene polymer (F) containing 0.1 mmol / g or more of the hydrolyzable silicon group represented by the general formula (1) in the side chain is mixed,
It is considered to exhibit extremely high storage stability.

Furthermore, the molecular weight distribution Mw / Mn (hereinafter abbreviated as molecular weight distribution Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.7 or less and the molecular weight is 8, By using 000 to 50,000 polyoxyalkylene polymer (A), a polymer (G) having low viscosity and excellent workability can be obtained.

Further, since the polyoxyalkylene polymer (A) further contains a hydrolyzable silicon group represented by the above general formula (1) together with the unsaturated group , the obtained polymer (G) Can itself be the curable composition (H). In this case, the flexible polyoxyalkylene polymer has a structure having a hydrolyzable silicon group at the terminal, and excellent physical properties can be obtained after curing. Furthermore, when the polyoxyalkylene polymer (F) is blended with this,
A bond is formed during curing between the hydrolyzable silicon group derived from the polyoxyalkylene polymer (A) and the hydrolyzable silicon group derived from the polyoxyalkylene polymer (F),
A remarkably excellent mechanical strength can be obtained.

Furthermore, by using at least one monomer (B) selected from alkyl acrylate and methacrylic acid alkyl monomers as the polymerizable monomer, the weather resistance is greatly improved. In addition, the adhesion of the acrylic paint to the surface of the cured product is also improved.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Polyoxyalkylene Polymer (A) The polyoxyalkylene polymer (A) having the characteristics 1) to 3) used in the present invention has a functional group as described below. It is preferable that the polyoxyalkylene polymer is used as a raw material, and an unsaturated group is introduced into a part or all of the terminal of the polyoxyalkylene polymer as a raw material.

In the present invention, it is particularly important that the polyoxyalkylene polymer (A) has an unsaturated group at the terminal or side chain. That is, when the polymerizable monomer is polymerized in the presence of the polyoxyalkylene polymer (A), the unsaturated group acts as a polymerizable unsaturated group, whereby the polyoxyalkylene polymer (A) is It is incorporated as a macromonomer in the form of being grafted to a polymer of a polymerizable monomer, and the polyoxyalkylene polymer (A) does not separate from the polymer of the polymerizable monomer and exhibits extremely high storage stability. it is conceivable that.

Further, the polyoxyalkylene polymer (A)
Can contain 0.01 mol / g or more of the hydrolyzable silicon group represented by the above general formula (1) together with the unsaturated group. In this case, a polyoxyalkylene polymer having both an unsaturated group and the hydrolyzable silicon group represented by the above general formula (1) in the molecule may be used.

In the present invention, the molecular weight of the polyoxyalkylene polymer (A) can be selected as appropriate depending on the application, but the molecular weight is preferably 8,000 to 50,000, and 8,000 to It is more preferably 20,000, particularly preferably 12,000 to 20,000. For applications such as sealants in which flexibility is important, the molecular weight is preferably 8,000 to 50,000, more preferably 8,000 to 25,000, and 12,000 to 20,000. Is most preferable. For applications such as adhesives that require strength, a polymer having a molecular weight of 8,000 to 30,000 is preferable.

When the molecular weight is less than 8,000, the cured product becomes brittle, and when it exceeds 30,000, the workability is remarkably deteriorated due to the high viscosity.

Raw material polyoxyalkylene polymer As the raw polyoxyalkylene polymer of the above polyoxyalkylene polymer (A), those having the following characteristics I) to III) are preferable.

I) Hydroxyl-terminated one produced by reacting cyclic ether in the presence of catalyst and initiator II) Molecular weight 8,000-50,000 III) Molecular weight distribution Mw / Mn is 1.7 or less As the initiator, a hydroxy compound having one or more hydroxyl groups can be used.

As the above catalyst, a composite metal cyanide is used.
A compound complex catalyst is used. The complex metal cyanide complex is preferably a complex containing zinc hexacyanocobaltate as a main component, and particularly preferably an ether and / or alcohol complex, the composition of which is essentially JP-B-46-272.
Those described in Japanese Patent Publication No. 50 can be used. In this case, as the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. Further, t-butanol is preferable as the alcohol.

Examples of the above cyclic ethers include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, hexylene oxide and tetrahydrofuran. These are 1
One kind or two or more kinds can be used.

[0037]

Polyoxypropylene polyols having 2 to 6 valences are more preferable, and polyoxypropylene diol and polyoxypropylene triol are particularly preferable. In addition, unsaturated group-terminated polyoxyalkylene polymers such as allyl-terminated polyoxypropylene monool can also be used.

The molecular weight distribution Mw / Mn is more preferably 1.6 or less, and particularly preferably 1.5 or less. If the number average molecular weight (Mn) is the same, Mw
The smaller / Mn, the polyoxyalkylene polymer (A)
Has a low viscosity, and the polymer (G) of the present invention obtained by polymerizing a polymerizable monomer in the presence of the polyoxyalkylene polymer (A) also has a low viscosity, so that the workability is excellent.

In particular, when the flexibility of the cured product is increased, the number of hydroxyl groups is 2 or 3, and when good adhesiveness and curability are obtained, the number of hydroxyl groups is preferably 3-8. .

Method of Introducing Unsaturated Group into Raw Polyoxyalkylene Polymer The polyoxyalkylene polymer (A) in the present invention is
It can be obtained by using a polyoxyalkylene polymer having a hydroxyl group as described above as a raw material and further partially or entirely making the terminal an unsaturated group.

The method of introducing the unsaturated group into the raw material polyoxyalkylene polymer is not particularly limited, but for example,
Examples thereof include a method in which a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene polymer having a hydroxyl group, and bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond or the like.
In addition, there is also a method of introducing an unsaturated group into a side chain by adding an unsaturated group-containing epoxy compound such as allyl glycidyl ether and copolymerizing it when polymerizing a cyclic ether.

Specifically, a method of reacting the terminal hydroxyl group of the polyoxyalkylene polymer with an alkali metal or an alkali metal compound to convert it into an alkoxide group, and then reacting it with a halogen compound having an unsaturated group can be mentioned.

The unsaturated group is preferably an alkenyl group, but is not limited thereto. Alkenyl groups include allyl group, isopropenyl group, 1
An alkenyl group having 6 or less carbon atoms such as a butenyl group is preferable, and an allyl group is most preferable. And as the halogen compound having an unsaturated group, allyl chloride or the like is preferable.
Also in this case, the alkenyl group is bonded to the polyalkylene oxide polymer via the etheric oxygen atom.

Hydrolyzable Silicon Group and Method for Introducing It If the polyoxyalkylene polymer (A) contains the hydrolyzable silicon group represented by the above general formula (1) , the hydrolyzable silicon group is contained. Depending on the amount, it will itself be a curable polymer. Since this curable polymer has a structure having a hydrolyzable silicon group at the end of the flexible polyoxyalkylene polymer, it has excellent physical properties after curing.

The polyoxyalkylene polymer (A) is
0.01 mm of the hydrolyzable silicon group represented by the above general formula (1) at the end or side chain of the molecular chain together with the unsaturated group
ol / g or more is contained . Further, in the general formula (1), a is more preferably a hydrolyzable silicon group represented by 2 or 3.

In the above general formula (1), the hydrolyzable silicon group represented by a of 2 is preferably a dialkoxyalkylsilyl group having an alkoxy group in which X is 4 or less, and a dimethoxymethylsilyl group. Most preferred.

In the above-mentioned general formula (1), the hydrolyzable silicon group in which a is 3 is preferably a trialkoxysilyl group in which X is an alkoxy group having 4 or less carbon atoms. The trialkoxysilyl group has an extremely high reaction rate in the initial stage of the silanol group generation reaction as compared with an alkyldialkoxysilyl group or a dialkylalkoxysilyl group, and therefore a polymer having a trialkoxysilyl group is extremely reactive, The initial curing speed is very fast. Therefore, when the polymer (G) of the present invention has a trialkoxysilyl group, the curable composition (H) containing the polymer (G) exhibits sufficient strength characteristics in a short time, and particularly It is considered to have the effect of shortening the time until the development of adhesiveness. Further, of the trialkoxysilyl groups, the trialkoxysilyl group having an alkoxy group having a small number of carbon atoms has a faster reaction rate in the initial stage of the silanol group generation reaction than the trialkoxysilyl group having an alkoxy group having a large number of carbon atoms. Therefore, it is preferable. That is, a trimethoxysilyl group and a triethoxysilyl group are preferable, and a trimethoxysilyl group is most preferable because the reaction rate in the initial stage of the silanol group generation reaction is extremely high.

Therefore, in the above general formula (1),
As the hydrolyzable silicon group represented by a of 3, a trimethoxysilyl group is most preferable.

As will be described later, the hydrolyzable silicon group is usually introduced into the raw material polyoxyalkylene polymer via an organic group.

That is, the hydrolyzable silicon group contained in the polyoxyalkylene polymer (A) is represented by the following general formula (2).
It is preferable to have a group represented by

General formula: —R ⁰ —SiX _a R ¹ _3-a (2) (R ⁰ : divalent organic group, R ¹ , X, a: same as general formula (1).)

Here, R ¹ in the above general formula (2) 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 fluoro group. An alkyl group, particularly preferably a methyl group,
Examples thereof include ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and phenyl group. When there are a plurality of R ^1's , they may be the same or different.

Further, as the hydrolyzable group in X,
For example, a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, a carbamoyl group, an amino group,
Examples thereof include an aminooxy group and a ketoximate group. Among these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. That is, as preferable X, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group, particularly a methoxy group, an ethoxy group, a propoxy group or a propenyloxy group can be exemplified. Also, when there are a plurality of Xs,
They may be the same or different.

In the present invention, the number of hydrolyzable silicon groups in one molecule of the polyoxyalkylene polymer is 1.
It is preferable that it is -8, and it is especially preferable that it is 2-6. When the number of hydrolyzable silicon groups is out of the above range, the flexibility of the cured product is reduced, which is not preferable.

Method for Introducing Hydrolyzable Silicon Group into Raw Material Polyoxyalkylene Polymer The method for introducing the above hydrolyzable silicon group into the raw material polyoxyalkylene polymer is not particularly limited, and, for example, the following (a) It can be introduced by the method (d).

(A) After introducing an ethylenically unsaturated group at the terminal of the polyoxyalkylene polymer having a hydroxyl group,
A method of reacting a hydrosilyl compound represented by the following general formula (3).

General formula: HSiX _a R ¹ _3-a (3) (R ¹ , X, a: same as general formula (1))

When the above hydrosilyl compound is reacted, catalysts such as platinum-based catalysts, rhodium-based catalysts, cobalt-based catalysts, palladium-based catalysts, nickel-based catalysts, etc. can be used, but chloroplatinic acid, platinum metal, platinum chloride, Platinum based catalysts such as platinum olefin complexes are preferred. The reaction for reacting the hydrosilyl compound is preferably carried out at 30 to 150 ° C, preferably 60 to 120 ° C for several hours.

(B) A method of reacting a terminal of a polyoxyalkylene polymer having a hydroxyl group with a compound represented by the following general formula (4).

General formula: R ¹ _3-a —SiX _a —R ² NCO (4) (R ¹ , X, a: same as general formula (1). R ² : carbon number 1 to 1
17 divalent hydrocarbon groups. )

In the above reaction, a known urethanization catalyst may be used, and the above reaction is preferably carried out at 20 to 200 ° C., preferably 50 to 150 ° C. for several hours.

(C) After the end of the hydroxyl group-containing polyoxyalkylene polymer is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the isocyanate group is represented by the following general formula (5). A method of reacting a W group of a silicon compound.

General formula: R ¹ _3-a —SiX _a —R ² W (5) (R ¹ , R ² , X, a: same as general formula (1) W: hydroxyl group, carboxyl group, mercapto group And an active hydrogen-containing group selected from an amino group (primary or secondary).)

(D) After introducing an unsaturated group into the terminal of the polyoxyalkylene polymer having a hydroxyl group by the above-mentioned method, the olefin group and the above general formula (5)
A method in which W is a mercapto group of a silicon compound represented by a mercapto group.

In the above general formula (5), as the silicon compound in which W is represented by a mercapto group, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3- Examples thereof include mercaptopropyltriethoxysilane.

At the time of 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 the polymerization initiator.

Examples of the above-mentioned polymerization initiator include peroxide-based, azo-based, or redox-based polymerization initiators and metal compound catalysts, and specifically, 2,2′-azobisisobutyronitrile. , 2,2'-azobis (2-
Methyl butyronitrile), benzoyl peroxide, t
-Butyl peroxide, acetyl peroxide, diisopropyl peroxydicarbonate and the like. The above reaction is carried out at 20 to 200 ° C, preferably 50 to 15
It is preferred to carry out at 0 ° C. for several hours to several tens of hours.

In the above method, the order of introducing the unsaturated group and the hydrolyzable silicon group is not particularly limited,
In the methods (a) and (d), it is easy to introduce an unsaturated group at the end of the polyoxyalkylene polymer having a hydroxyl group and then convert a part of the unsaturated group into a hydrolyzable silicon group to facilitate the process. Can be introduced. Further, in the methods (b) and (c), if necessary, a part of the hydroxyl groups of the polyoxyalkylene polymer having a hydroxyl group is converted to an unsaturated group, and the remaining hydroxyl group is utilized to make a hydrolyzable silicon group. And the like.

Polymerizable Monomer In the present invention, the polymerizable monomer is selected from acrylic acid alkyl ester and methacrylic acid alkyl ester (hereinafter abbreviated as (meth) acrylic acid alkyl ester) monomers. At least one kind of monomer (B) is used. As the monomer (B), a compound represented by the following general formula (6) is preferable.

General formula: CH ₂ ═CR ⁴ COOR ³ (6) (R ⁴ : hydrogen atom or methyl group, R ³ : hydrogen atom or monovalent organic group)

R ³ preferably has a hydrogen atom or an alkyl group having 1 or more carbon atoms.

That is, as the monomer (B), R
^At least one monomer (D) selected from (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms as ³ , and an alkyl group having 10 or more carbon atoms as R ³ (meth) It is preferable to use at least one monomer (E) selected from alkyl acrylates.

Further, as the above-mentioned monomer (D), those having an alkyl group having 1 to 4 carbon atoms are particularly preferable. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, but (meth) acrylic Methyl acid and butyl (meth) acrylate are particularly preferred. The monomer (D) may be used alone or in combination of two or more kinds.

As the above-mentioned monomer (E), those having an alkyl group having 10 to 30 carbon atoms are more preferable,
Those having an alkyl group having 10 to 20 carbon atoms are particularly preferable. Specific examples include lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and the like. The above monomer (E) may be used alone or in combination of two or more kinds.

In the present invention, when the above monomers (D) and (E) are used in combination, the proportion thereof can be adjusted arbitrarily, but from the viewpoint of storage stability and mechanical properties of the cured product, a single amount by weight is used. Body (D) / monomer (E) is 95 / 5-40 / 6
It is preferably 0, more preferably 90/10 to 40/60.

Next, the polymerizable unsaturated group-containing monomer (C) is preferably a compound represented by the following general formula (7). The polymerizable unsaturated group-containing monomer (C) is a compound other than the polyoxyalkylene polymer (A).

General formula: CRR ⁷ = CR ⁵ R ⁶ (7) (R, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or a monovalent organic group.)

[0079] Then, R, substituted monovalent C1-10 as the organic group for R ^7, or is preferably unsubstituted hydrocarbon group, R, can R ⁷ are each hydrogen atom More preferable.

The organic group for R ⁵ and R ⁶ is a monovalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms,
It is preferably an alkoxy group, a cyano group, a cyano group-containing group, an alkenyl group, an acyloxy group, a carbamoyl group, a pyridyl group, a glycidyloxy group or a glycidyloxycarbonyl group. Particularly, R ⁵ is preferably a hydrogen atom, a halogen atom or a monovalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.

Specifically, specifically, styrene-based monomers such as styrene, α-methylstyrene and chlorostyrene;
Cyano group-containing monomers such as acrylonitrile and 2,4-dicyanobutene-1; vinyl ester-based monomers such as vinyl acetate and vinyl propionate; butadiene, isoprene,
Diene monomers such as chloroprene; glycidyl group-containing monomers such as vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and other olefins, unsaturated esters, halogenated olefins , Vinyl ether; etc., but a cyano group-containing monomer, a glycidyl group-containing monomer or a styrene-based monomer is preferable. In particular, the use of acrylonitrile, glycidyl acrylate, glycidyl methacrylate, or styrene is preferable because it exhibits more excellent adhesiveness and mechanical properties.

The polymerizable unsaturated group-containing monomer (C) may be used alone or in combination of two or more kinds.

In the present invention, when the polymerizable monomer comprises the above-mentioned monomers (B) and (C), high weather resistance and good adhesion of the acrylic coating to the surface of the cured product (meta)
In order to strongly reflect the characteristics of the acrylic acid alkyl ester monomer as a polymer, the proportion of the monomer (B) is 50% by weight of the total amount of the monomers (the sum of (B) and (C)). It is preferably not less than 70% by weight, more preferably not less than 70% by weight.

Production Method of Polymer (G) The polymer (G) of the present invention is prepared by polymerizing the above-mentioned polymerizable monomer in the presence of the polyoxyalkylene polymer (A) as described above, optionally in the presence of a solvent. It can be obtained by polymerizing the monomer and removing a part or all of the solvent by distillation or the like, if necessary.

Polymerization in the presence of a polyoxyalkylene polymer (A) and a polyoxyalkylene polymer having no unsaturated group (for example, a polyoxyalkylene polymer having a hydrolyzable silicon group at the terminal). You may go.

Although the solvent can be arbitrarily selected, examples thereof include hydrocarbons, ethers and acetic acid esters, and specific examples thereof include xylene, toluene and 2-methoxy-2-methylpropane.

The polymerization can be carried out by a known method, and a polymerization initiator such as a radical generator may be used, and in some cases, the polymerization may be performed by radiation or heat without using the polymerization initiator. The polymerization initiator, the polymerization temperature, the polymerization time, and the like are preferably the same as the conditions described in (d) above.

In the present invention, the polyoxyalkylene polymer (A) and the polymerizable monomer ((B) + (C)) are mixed in a weight ratio of polyoxyalkylene polymer (A) /
The polymerizable monomer is preferably used in the range of 100/1 to 1/300, and is 100/100 from the viewpoint of workability and the like.
It is particularly preferably used in the range of 1/1/100, and further 100/1 to 1/10.

The state of the polymer (G) may be a state in which the polymer fine particles are uniformly dispersed in the polyoxyalkylene polymer (A) or a state in which the polymer (G) is uniformly dissolved.

Polymer (G) The polymer (G) of the present invention contains a hydrolyzable silicon group . Polymer (G) containing hydrolyzable silicon group
Can be obtained by using a polymer having a hydrolyzable silicon group as the polyoxyalkylene polymer (A). Further, the polyoxyalkylene polymer (A)
When does not have a hydrolyzable silicon group, a polymer (G) containing a hydrolyzable silicon group can be obtained by further modifying by the following methods (e) to (i). .

(E) In the presence of the polyoxyalkylene polymer (A) containing an unsaturated group, the monomer (B),
Alternatively, after polymerizing the monomer (B) and the polymerizable unsaturated group-containing monomer (C), the residual unsaturated group in the obtained polymer is hydrolyzed by the general formula (1). Method of converting into crystalline silicon group.

The above conversion method is preferably a method in which an unsaturated group is reacted with the hydrosilyl compound represented by the general formula (3).

(F) When the monomer (B) or the monomer (B) and the polymerizable unsaturated group-containing monomer (C) are polymerized, a polymerizable monomer having a hydrolyzable silicon group is further added. A method of copolymerizing a monomer.

As the polymerizable monomer having a hydrolyzable silicon group, a polymerizable monomer having a hydrolyzable silicon group represented by the above general formula (1) is preferable, and particularly, the following general formula (8) The compound represented by these is preferable.

General formula: R ⁹ —SiY _b R ⁸ _3-b (8) (R ⁹ : monovalent organic group having a polymerizable unsaturated group, R ⁸ : substituted or non-substituted with 1 to 20 carbon atoms) Substituted monovalent organic group, Y:
Hydroxyl group or hydrolyzable group, an integer of b: 1 to 3. However,
When a plurality of R ⁸ 's are present, those R ⁸ 's may be the same or different. When there are a plurality of Y's, those Y's may be the same or different. )

That is, examples of the polymerizable monomer having a hydrolyzable silicon group include a vinyl monomer having a hydrolyzable silicon group and an acrylic monomer having a hydrolyzable silicon group. Specifically, vinylsilanes such as vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and tris (2-methoxyethoxy) vinylsilane; 3- Examples thereof include acryloyloxysilanes such as (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxysilane; methacryloyloxysilanes. Particularly preferred is 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane.

Other examples of the polymerizable monomer having a hydrolyzable silicon group include, for example, 2 to 30 silicon atoms.
It is also possible to use a polysiloxane compound having a carbon-carbon double bond and a silicon atom bonded to a hydrolyzable group.

Only one kind of these polymerizable monomers having a hydrolyzable silicon group may be used, or two or more kinds may be used in combination. It is preferable to use 0.01 to 20 parts by weight in parts. If it is out of the above range, the effect of improving the physical properties of the cured product is inferior, which is not preferable.

(G) As a polymerizable unsaturated group-containing monomer (C), a polymerizable monomer having a reactive functional group is used for polymerization, and then the reactivity of the resulting polymer is improved. A method of reacting a functional group with a compound having a hydrolyzable silicon group capable of reacting with this functional group.

The polymerizable monomer having a reactive functional group is preferably one having a hydroxyl group or an unsaturated group, and the compound having a hydrolyzable silicon group is represented by the above general formula (1). Those having a hydrolyzable silicon group are preferable.

(H) A method of carrying out polymerization using a radical polymerization initiator having a hydrolyzable silicon group.

As the radical polymerization initiator having a hydrolyzable silicon group, an azo compound or a peroxide compound having a group represented by the general formula (1) is particularly preferable.

(I) A method of polymerizing using a chain transfer agent having a hydrolyzable silicon group. The chain transfer agent having a hydrolyzable silicon group,
Those having a group represented by the above general formula (1) are particularly preferable, and specific examples thereof include a mercapto compound, an amino compound, a bromine compound and the like having a group represented by the above general formula (1).

Further, the polymer (G) of the present invention may contain a hydroxyl group in addition to the hydrolyzable silicon group. in this case,
The hydroxyl group reacts with the hydrolyzable silicon group in the presence of a curing catalyst and crosslinks with an alkoxysilyl bond, thereby contributing to the curing reaction.

The method of introducing a hydroxyl group into the polymer (G) of the present invention includes a method of using a polyoxyalkylene polymer (A) having a hydroxyl group at the terminal in addition to an unsaturated group, and a polymerizable monomer. Examples include a method of using a polymerizable monomer having a hydroxyl group as a body.

The polyoxyalkylene polymer (A) having a hydroxyl group at the terminal in addition to the above-mentioned unsaturated group is, for example, a hydroxyl group at the time of introducing an unsaturated group into the above-mentioned starting polyoxyalkylene polymer having a hydroxyl group. It can be easily obtained by introducing an unsaturated group by binding it with an ether bond, an ester bond, a urethane bond, a carbonate bond or the like so that a part thereof remains. Further, when the polymerizable monomer is polymerized, a polymerizable monomer having a hydroxyl group may be further added and copolymerized.

Examples of the polymerizable monomer having a hydroxyl group include a vinyl monomer having a hydroxyl group and an acrylic monomer having a hydroxyl group. Specific examples include hydroxybutyl vinyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, and the like.

The above-mentioned polymerizable monomer having a hydroxyl group may be used alone or in combination of two or more kinds. In that case, it is preferable that 0. 01-2
It is preferable to use 0 part by weight. If it is out of the above range, the effect of improving the physical properties of the cured product is inferior, which is not preferable.

-Curable composition (H) Next, the curable composition (H) which is another embodiment of the present invention will be described. The curable composition (H) of the present invention contains, among the above-mentioned polymers (G), a polymer (G) containing a hydrolyzable silicon group, or a polymer (G) and a main chain. Containing a polyoxyalkylene polymer (F) containing 0.1 mmol / g or more of the hydrolyzable silicon group represented by the above general formula (1) at the terminal and / or side chain of the above, and a curing accelerating catalyst. Is.

Polyoxyalkylene Polymer (F) The above polyoxyalkylene polymer (F) can be cured at room temperature, and since the cured product has flexible rubber elasticity, it is suitable for applications such as adhesives and waterproof materials. It is widely used.

The polyoxyalkylene polymer (F) may have various structures, but by selecting and combining the structures according to the intended use and the desired physical properties, the characteristics of the curable composition can be easily obtained. Can be adjusted to.

As described above, the polymer (G) of the present invention is considered to be the polyoxyalkylene polymer (A) incorporated as a macromonomer in the form of being grafted to a polymerizable monomer. Since the polyoxyalkylene polymer (F) has the same structure as the polyoxyalkylene polymer (A) which is this graft polymer,
It is difficult to separate even when blended with the polymer (G), and exhibits high storage stability.

Examples of such a polyoxyalkylene polymer (F) include, for example, JP-A-3-47825, JP-A-3-72527, and JP-A-3-7962.
Examples thereof include those described in Japanese Patent Publication No. 7 and the like.

Further, the polyoxyalkylene polymer (F)
Is preferably produced by using a polyoxyalkylene polymer having a functional group as a raw material and introducing a hydrolyzable silicon group into the terminal or side chain thereof with or without an organic group.

The above-mentioned raw material polyoxyalkylene polymer is not particularly limited in terms of molecular weight, molecular weight distribution and the like, but it is the same as the above-mentioned raw material polyoxyalkylene polymer of the polyoxyalkylene polymer (A). Obtained, molecular weight 8,000-50,000, molecular weight distribution Mw
It is preferable to use a high molecular weight polyoxyalkylene polymer having / Mn of 1.7 or less, preferably 1.6 or less, more preferably 1.5 or less.

If the raw material polyoxyalkylene polymer has the same number average molecular weight (Mn), the smaller the Mw / Mn, the lower the viscosity of the polyoxyalkylene polymer (F) obtained from it. Even if it has excellent workability and has the same elastic modulus when cured, the cured product has large elongation and high strength. Therefore, when it is included in the polymer (G), it has excellent physical properties and workability. A composition (H) can be obtained.

The details of the method of introducing a hydrolyzable silicon group into the terminal or side chain of the starting polyoxyalkylene polymer are the same as those described for the polyoxyalkylene polymer (A).

In the present invention, the molecular weight of the polyoxyalkylene polymer (F) can be selected as appropriate depending on the application, but the molecular weight is preferably 8,000 to 50,000, and 8,000 to 8,000. It is more preferably 20,000, particularly preferably 12,000 to 20,000. For applications such as sealants in which flexibility is important, the molecular weight is preferably 8,000 to 50,000, more preferably 8,000 to 25,000, and 12,000 to 20,000. Is most preferable. For applications such as adhesives that require strength, a polymer having a molecular weight of 8,000 to 30,000 is preferable.

When the molecular weight is less than 8,000, the cured product becomes brittle, and when it exceeds 30,000, the workability is remarkably deteriorated due to the high viscosity.

When the cured composition (H) contains the polyoxyalkylene polymer (F) and the polymer (G), the mixing ratio thereof is the polyoxyalkylene polymer (F) in a weight ratio. ) / Polymer (G) is 1/10 to 10
It is preferably in the range of / 1.

Further, the curable composition (H) of the present invention is hard.
Includes a catalyst for promoting chemical conversion. Further, a filler as shown below,
It may contain a plasticizer, an adhesiveness-imparting agent, a solvent, a dehydrating agent, a thixotropic agent, an antiaging agent and other additives.

(Filler) As the filler, known fillers can be used. Specifically, calcium carbonate whose surface is surface-treated with a fatty acid or a resin acid organic compound, and an average particle obtained by further pulverizing the calcium carbonate Colloidal calcium carbonate having a diameter of 1 μm or less, light calcium carbonate having an average particle size of 1 to 3 μm produced by a precipitation method, calcium carbonate such as heavy calcium carbonate having an average particle size of 1 to 20 μm, fumed silica, precipitable silica, anhydrous silica. Acid, 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 white, shirasu balloon, glass balloon, wood powder , Pulp, cotton chips, mica, walnut flour, rice flour, graphite, fine aluminum powder, furin Powdery fillers such as powders; fibrous fillers such as asbestos, glass fibers, glass filaments, carbon fibers, Kevlar fibers, polyethylene fibers; and the like, and these may be used alone or in combination of two or more kinds. You may.

When a filler is used, its amount is from 0.001 to 100 parts by weight based on 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 1,000 parts by weight, particularly preferably 50 to 250 parts by weight.

(Plasticizer) As the plasticizer, known plasticizers can be used. Specifically, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate and diisononyl phthalate; dioctyl adipate. ,
Aliphatic carboxylic acid esters such as bis (2-methylnonyl) succinate, dibutyl sebacate and butyl oleate;
Alcohol esters such as pentaerythritol ester; Phosphate esters such as trioctyl phosphate, tricresyl phosphate; Epoxidized soybean oil, Dioctyl 4,5-epoxyhexahydrophthalate, Epoxy plasticizer such as benzyl epoxy stearate; Chlorine Paraffin; polyester-based plasticizers such as polyesters obtained by reacting a dibasic acid with a dihydric alcohol; polyethers such as polyoxypropylene glycol and its derivatives; poly-α-
Polymeric plasticizers such as styrene-based oligomers such as methylstyrene and polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene and other oligomers; and the like. However,
It can be appropriately selected according to the use and purpose. For example, when it is desired to improve weather resistance, a so-called polymer plasticizer such as a polyoxyalkylene polyol having a large molecular weight and / or an alkyl ether of a hydroxyl group thereof is used, and in the case of an adhesive application, a plasticizer is used. Is not always necessary, but rather the adhesiveness can be improved by using a non-plasticized composition that does not use a plasticizer.

When a plasticizer is used, the amount thereof is 0.001 to 100 parts by weight based on 100 parts by weight of the polymer (G) or the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 1,000 parts by weight.

(Curing Accelerating Catalyst) In the present invention, when the curable composition is cured, it is cured.
Uses a promoted catalyst. Specifically, metal salts such as alkyl titanates, organosilicon titanates and bismuth tris (2-ethylhexanoate); acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid; butylamine,
Aliphatic monoamines such as hexylamine, octylamine, decylamine, dodecylamine; ethylenediamine,
Aliphatic diamines such as hexamethylenediamine; Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine; Heterocyclic amines such as piperidine and piperazine; Aromatic amines such as m-phenylenediamine; Ethanolamine , Triethylamine, amine compounds such as various modified amines used as a curing agent for epoxy resins; divalent tin compounds such as tin 2-ethylhexanoate, tin naphthenate, tin stearate and the above amines; dibutyltin di acetate, dibutyltin dilaurate, mixture of dioctyl tin dilaurate, carboxylic acid type organic tin compound and these carboxylic acid type organic tin compound and the amines of the _{following; (n-C 4 H 9} ) 2 Sn (OCOCH = CHCOOCH 3 )
_{2 (n-C 4 H 9} ) 2 Sn (OCOCH = CHCOOC 4 H 9
_{-N) 2 (n-C 8} H 17) 2 Sn (OCOCH = CHCOOC
_{H 3) 2 (n-C} 8 H 17) 2 Sn (OCOCH = CHCOOC 4 H 9
_{-N) 2 (n-C 8} H 17) 2 Sn (OCOCH = CHCOOC 8 H
_17- iso) ₂ The following sulfur-containing organotin compounds: (n-C ₄ H ₉ ) ₂ Sn (SCH ₂ COO) (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO) (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO) (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ OC
_{OCH 2 S) (n-C} 4 H 9) 2 Sn (SCH 2 COOC 8 H 17 -is
_{o) 2 (n-C 8} H 17) 2 Sn (SCH 2 COOC 8 H 17 -is
_{o) 2 (n-C 8} H 17) 2 Sn (SCH 2 COOC 8 H 17 -n) 2 (n-C 4 H 9) 2 SnS (n-C 4 H 9) 2 SnO, (n-C 8 H ₁₇ ) ₂ SnO and other organic tin oxides, and these organic tin oxides,
Reaction products with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate; chelate tin compounds below and tin compounds thereof with alkoxysilanes the reaction product (wherein, acac represents an acetylacetonato _{ligand); (n-C 4 H} 9) 2 Sn (acac) 2 (n-C 8 H 17) 2 Sn (acac) 2 (n-C _{4 H 9) 2 (C 8} H 17 O) Sn (acac) tin compounds of the _{following; (n-C 4 H 9} ) 2 (CH 3 COO) SnOSn (OCOC
_{H 3) (C 4 H 9} -n) 2 (n-C 4 H 9) 2 (CH 3 O) SnOSn (OCH 3)
(C ₄ H ₉ -n) but ₂ and the like, one or more of them are used.

The amount of the curing accelerating catalyst used is 0.0001 to 10 parts by weight based on 100 parts by weight of the total of the polymer (G) or the polymer (G) and the polyoxyalkylene polymer (F). Preferred .

(Adhesiveness imparting agent) An adhesiveness imparting agent is used for the purpose of improving the adhesiveness. As these adhesiveness-imparting agents, a silane coupling agent or an epoxy resin may be added, and an epoxy resin curing agent may be used together if necessary.

As the silane coupling agent, (meth) acryloyloxy group-containing silanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane; 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-
Amino group-containing silanes such as aminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane; 3
-Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane; 3-glycidyloxypropyltrimethoxysilane, 3- Epoxy group-containing silanes such as glycidyloxypropylmethyldimethoxysilane and 3-glycidyloxypropyltriethoxysilane; 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (N- Carboxylmethyl-2-aminoethyl) -3-aminopropyltrimethoxysilane and other carboxyl group-containing silanes; and the like.

A reaction product obtained by reacting two or more kinds of the above silane coupling agents may be used.
Reaction product of amino group-containing silanes and epoxy group-containing silanes, reaction product of amino group-containing silanes and (meth) acryloyloxy group-containing silanes, reaction product of epoxy group-containing silanes and mercapto group-containing silanes , Reaction products of mercapto group-containing silanes, and the like. These reactants are mixed at room temperature to
It can be easily obtained by stirring at 150 ° C. for 1 to 8 hours. The above reactants may be used alone or 2
You may use together more than one kind.

When the silane coupling agent or the above reaction product is used, the amount of the silane coupling agent used is 10 in total of the polymer (G) or the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 0.001 to 30 parts by weight with respect to 0 parts by weight.

As the epoxy resin, a general epoxy resin is used. Specifically, bisphenol A-
Diglycidyl ether type epoxy resin; Bisphenol F-diglycidyl ether type epoxy resin; Flame retardant type epoxy resin such as tetrabromobisphenol A-glycidyl ether type epoxy resin; Novolac type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Bisphenol A / Propylene oxide adduct glycidyl ether type epoxy resin; 4-glycidyloxybenzoic acid glycidyl, diglycidyl phthalate, tetrahydrophthalic acid diglycidyl, hexahydrophthalic acid diglycidyl diglycidyl ester epoxy resin; m-aminophenol epoxy resin Diaminodiphenylmethane-based epoxy resin; Urethane-modified epoxy resin; Various alicyclic epoxy resins; 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; epoxidized unsaturated polymer such as petroleum resin; Examples thereof include epoxy resins and vinyl polymers containing an epoxy group.

When an epoxy resin or a vinyl polymer containing an epoxy group is used, the amount thereof is 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F). It is preferably 0 to 100 parts by weight.

When the curing agent (or curing catalyst) for the epoxy resin is used in combination, the curing agent may be a commonly used curing agent for epoxy resin. Specifically, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6. Amines such as tris (dimethylaminomethyl) phenol or salts thereof; blocked amines such as ketimine compounds; polyamide resins; imidazoles; dicyandiamides;
Boron trifluoride complex compounds; carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, pyromellitic anhydride; phenoxy resins; carboxylic acids; alcohols A polyalkylene oxide polymer having an average of at least one group capable of reacting with an epoxy group in the molecule (terminal aminated polyoxypropylene glycol, terminal carboxylated polyoxypropylene glycol, etc.);
Examples thereof include liquid terminal functional group-containing polymers such as polybutadiene having a terminal modified with a hydroxyl group, a carboxyl group, an amino group, hydrogenated polybutadiene, an acrylonitrile-butadiene copolymer, an acrylic polymer; and a ketimine compound.

When the curing agent (or curing catalyst) for the epoxy resin is used in combination, the amount used is preferably 0.1 to 300 parts by weight based on the epoxy resin.

(Solvent) A solvent may be added for the purpose of adjusting the viscosity and improving the storage stability of the composition.

Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols and ketone ethers. , Ketone esters and ester ethers can be used.

Particularly, alcohols are preferable because the addition of the alcohols improves the storage stability of the curable composition (H) of the present invention. Alcohols have 1 carbon
Alkyl alcohols of 10 are preferred, methanol,
Particularly preferred are ethanol, isopropanol, isopentyl alcohol, hexyl alcohol and the like.

When a solvent is used, its amount is 0.001 to 50 with respect to 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 0 part by weight.

(Dehydrating Agent) In order to further improve the storage stability of the curable composition (H) of the present invention, a small amount of a dehydrating agent can be added within the range that does not adversely affect the curability and flexibility.

Specifically, alkyl orthoformates such as methyl orthoformate and ethyl orthoformate; methyl orthoacetate,
Alkyl orthoacetates such as ethyl orthoacetate; hydrolyzable organosilicon compounds such as methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane; hydrolyzable organotitanium compounds; Methoxysilane and tetraethoxysilane are particularly preferable in terms of cost and effect.

When a dehydrating agent is used, its amount is 0.001 to 3 with respect to 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 0 part by weight.

(Thixotropic agent) A thixotropic agent may be used for improving the sagging property. As such a thixotropic agent, hydrogenated castor oil, fatty acid amide and the like are used.

When the thixotropic agent is used, the amount thereof is 0 to 100 parts by weight of the total of the polymer (G) or the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 30 parts by weight.

(Anti-aging agent) As the anti-aging agent, generally used antioxidants, ultraviolet absorbers and light stabilizers are appropriately used. Hindered amine-based, benzotriazole-based, benzophenone-based, benzoate-based, cyanoacrylate-based, acrylate-based, hindered phenol-based, phosphorus-based, and sulfur-based compounds can be appropriately used.

When the antiaging agent is used, its amount is 0 to 1 with respect to 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 0 part by weight.

(Other Additives) An air oxidation curable compound or a photocurable compound may be added for the purpose of improving the adhesion and surface tack of the coating material for a long period of time. When they are used, the amount used is 10 in total of the polymer (G) or the polymer (G) and the polyoxyalkylene polymer (F).
It is preferably 0.001 to 50 parts by weight with respect to 0 parts by weight.

Examples of such air-oxidation-curable compounds include dry oils represented by tung oil, linseed oil, etc., various alkyd resins obtained by modifying the compounds, acrylic polymers modified with the dry oils, and silicones. Resins, polybutadiene, diene-based polymers such as C5-8 diene polymers and copolymers, and various modified products of these polymers and copolymers (maleization modification, boiling oil modification, etc.) Can be mentioned. Polyfunctional acrylates are usually used as the photocurable compound.

Further, for the purpose of adjusting the modulus of the cured product and the tackiness of the surface, a compound having one silanol group in the molecule or a compound capable of forming a compound having one silanol group in the molecule is added. can do. By adding these compounds, the effect of reducing the modulus can be obtained without deteriorating the stickiness of the surface.

Examples of the compound having one silanol group in the molecule include trimethylsilanol, triethylsilanol, triphenylsilanol and the like.

As the compound capable of forming the compound having one silanol group in the molecule, hexamethyldisilazane, phenyloxytrimethylsilane, 2-
Examples thereof include ethylhexyloxytrimethylsilane, trimethylsilyl ether of 1,4-butanediol, and trimethylolpropane tristrimethylsilyl ether.

When a compound having a silanol group is used, the amount used is 0 to 10 parts by weight based on 100 parts by weight of the polymer (G) or the total of the polymer (G) and the polyoxyalkylene polymer (F). It is preferably part.

As the pigment, inorganic pigments such as iron oxide, chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green can be used.

[0154]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples.

The term "parts" means "parts by weight", and the "hydroxyl value-converted molecular weight" means the molecular weight converted from the hydroxyl value of the polyoxyalkylene polymer having a hydroxyl group as a raw material. The molecular weight distribution Mw / Mn is a value measured by gel permeation chromatography using tetrahydrofuran as a solvent. The calibration curve was created using polyoxyalkylene polyol.

Production Example 1 Hydroxyl number-converted molecular weight 17,000 obtained by reacting propylene oxide with glycerin as an initiator and in the presence of zinc hexacyanocobaltate-glyme complex catalyst, and molecular weight distribution Mw / Mn =
A methanol solution of sodium methoxide was added to 1.3 polyoxypropylene triol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene triol to sodium alkoxide. Then, react with allyl chloride to remove unreacted allyl chloride and purify the product to obtain an allyl group at the end of 0.20 mmol / g.
Polypropylene oxide (hereinafter referred to as P1) was obtained.

(Production Example 2) Propylene glycol was used as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst, and propylene oxide was reacted to obtain a hydroxyl value-converted molecular weight of 17,000 and a molecular weight distribution M.
Using polyoxypropylene glycol with w / Mn = 1.3, an allyl group was added to the end of 0.1 by the same method as in Production Example 1.
Polypropylene oxide having 5 mmol / g (hereinafter,
P2).

(Production Example 3) Polymer P obtained in Production Example 1
1, a hydrosilyl compound, methyldimethoxysilane, was reacted in the presence of a platinum catalyst, and a polypropylene oxide having a methyldimethoxysilyl group at the end of 0.14 mmol / g and an allyl group at 0.06 mmol / g (hereinafter referred to as P3) Got

Production Example 4 Polymer P obtained in Production Example 1
1, trimethoxysilane, which is a hydrosilyl compound, was reacted in the presence of a platinum catalyst, and a trimethoxysilyl group at the end was 0.14 mmol / g and an allyl group was 0.06 m.
Polypropylene oxide having mol / g (hereinafter P4
I got).

(Production Example 5) Polymer P obtained in Production Example 1
1, 2-mercaptopropyltrimethoxysilane, which is a silyl compound, is reacted with 2,2′-azobis (2-methylbutyronitrile), which is a polymerization agent, and a trimethoxysilyl group is added at the end of 0.14 mmol. / G, polypropylene oxide having an allyl group of 0.06 mmol / g (hereinafter referred to as P5) was obtained.

(Production Example 6) Polymer P obtained in Production Example 1
In comparison with 1, the molar ratio of hydrosilyl compound methyldimethoxysilane and trimethoxysilane was 30: 7.
The mixture mixed in a ratio of 0 was reacted in the presence of a platinum catalyst, and a total of 0.14 mmol / g of methyldimethoxysilyl group and trimethoxysilyl group and 0.0 of an allyl group were added to the terminals.
Polypropylene oxide having 6 mmol / g (hereinafter,
P6).

(Production Example 7) Polymer P obtained in Production Example 2
2, a hydrosilyl compound, methyldimethoxysilane, was reacted in the presence of a platinum catalyst, and a polypropylene oxide having a methyldimethoxysilyl group at the end of 0.12 mmol / g and an allyl group at 0.03 mmol / g (hereinafter referred to as P7). Got

(Production Example 8) Propylene oxide was polymerized in the presence of zinc hexacyanocobaltate-glyme complex catalyst using glycerin as an initiator to obtain a hydroxyl value-converted molecular weight of 10,000 and a molecular weight distribution Mw / Mn = 1. Three
After obtaining the polyoxypropylene triol of, it was purified. To this, γ-isocyanatopropyltrimethoxysilane was added to carry out a urethanization reaction, and a trimethoxysilyl group at the end was 0.28 mmol / g and an allyl group was at 0.0.
Polypropylene oxide having 5 mmol / g (hereinafter,
P8).

(Production Example 9) A sodium methoxide methanol solution 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 with heating. The terminal hydroxyl group was converted to sodium alkoxide. Next, after reacting with chlorobromomethane to increase the molecular weight,
Then, by reacting allyl chloride, polypropylene oxide having an allyloxy group at the end (molecular weight distribution Mw / M
n = 2.0) was obtained. Methyldimethoxysilane, which is a hydrosilyl compound, is reacted with this in the presence of a platinum catalyst,
0.14 mmol / methyldimethoxysilyl group at the end
g, a molecular weight of 9 having an allyl group of 0.08 mmol / g,
000 polypropylene oxide (hereinafter referred to as P9)
Got

Reference Examples 1 and 2 and Examples 3 and 4 As a graft polymer, 60 g of polypropylene oxide shown in Table 1 was placed in a reactor equipped with a stirrer, and toluene 1 was added.
20 g was added to dilute, and this mixture was uniformly mixed while heating at 100 ° C. The polymerizable monomers having the weight ratios shown in Table 1 were mixed with this so that the total amount was 40 g.
A solution in which 0.4 g of 2'-azobisisobutyronitrile was dissolved was added dropwise over 3 hours with stirring under a nitrogen atmosphere. After the dropping was completed, a toluene solution of 0.3 g of 2,2′-azobisisobutyronitrile was further dropped over 30 minutes, and then the mixture was heated and stirred at the same temperature for 3 hours. Toluene was distilled off from the obtained mixture under reduced pressure at 100 ° C. to obtain a polymer.

(Examples 5 to 8) As a graft polymer, 3 out of 60 g of polypropylene oxide shown in Table 2 was used.
0 g was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., a total of 4 parts by weight of polymerizable monomers in a weight ratio shown in Table 1
The mixture was mixed so as to be 0 g, and a mixture of a solution in which 0.8 g of 2,2′-azobisisobutyronitrile was dissolved and the remaining 30 g of polypropylene oxide was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of dropping, the mixture was heated and stirred at the same temperature for 1 hour. After completion of the reaction, add 1
Removal at 00 ° C. under reduced pressure gave a polymer. In addition, in Example 8, a mixture of P3: P4 (weight ratio) = 1: 1 was used.

Reference Examples 9 and 10 and Example 11 Polymers obtained in Reference Examples 1 and 2 and Example 3 , respectively,
The polypropylene oxide shown in Table 3 was used as the blend polymer, and the weight ratio of Reference Examples 9 and 10 was 40: 6.
0 and Example 11 were mixed at a weight ratio of 50:50 to obtain a composition.

(Comparative Example 1) As a graft polymer, 60 g of polypropylene oxide shown in Table 4 was placed in a reactor equipped with a stirrer and, while maintaining at 110 ° C, a polymerizable monomer having a weight ratio shown in Table 4 was added thereto. Mix so that the total amount becomes 40 g, and further add 2,2'-azobisisobutyronitrile 0.
A solution in which 4 g was dissolved was added dropwise over 3 hours with stirring under a nitrogen atmosphere. After the dropping was completed, a toluene solution of 0.32 g of 2,2'-azobisisobutyronitrile was further added dropwise over 30 minutes, and then heated and stirred at the same temperature for 3 hours to obtain a polymer.

(Comparative Examples 2 to 4) 50 g of xylene was placed in a reactor equipped with a stirrer, and while maintaining the temperature at 110 ° C., a polymerizable monomer having a weight ratio shown in Table 4 was mixed so that the total amount was 120 g. Then, a solution in which 3 g of 2,2′-azobisisobutyronitrile was further dissolved was added dropwise over 3 hours while stirring under a nitrogen atmosphere. After completion of dropping, the mixture was heated and stirred at the same temperature for 2 hours. The resulting copolymer was mixed with the polypropylene oxide shown in Table 4 as a blend polymer so that the resin solid content ratio was 40:60, and then xylene was distilled off under reduced pressure at 100 ° C. to obtain a composition. Obtained. In Comparative Example 3, a mixture of P8: P9 (weight ratio) = 1: 1 was used. In addition, the resin solid content refers to the one excluding the solvent.

(Test 1) Viscosity and storage stability of the polymers and compositions obtained in the above Examples , Reference Examples and Comparative Examples were measured as follows.

Viscosity: Each polymer and composition was placed in a 100 cc glass sample bottle and the viscosity was 25 using a B type viscosity type.
The viscosity was measured at ° C.

Storage stability: 100% of each polymer and composition
It was put in a cc glass sample bottle and stored at 70 ° C. for 2 months to see the appearance.

In addition, Examples 3 to 8 and Reference Examples 9 and 10,
To 100 parts of the polymers and compositions obtained in Example 11 and Comparative Examples 1 to 4, 100 parts of colloidal calcium carbonate, 50 parts of ground calcium carbonate, 50 parts of dioctyl phthalate.
Part, 3 parts of an aliphatic amide-type thixotropic agent, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane 2 parts, vinyltrimethoxysilane 1 part, benzotriazole-based light stabilizer 1 part, tertiary hindered amine-based light stabilizer 1 part, hindered phenol-based antioxidant 1 part , And 2 parts of dibutyltin bisacetylacetonate were added and mixed uniformly, and the mixture was filled in a cartridge for a sealing material capable of blocking moisture to obtain a curable composition. The curable composition was prepared by the following method. The weather resistance was checked with.

The curable composition was added to a thickness of 5 mm 1
After coating on an aluminum plate with a thickness of mm and curing at 20 ° C and 65% humidity for 7 days, and at 50 ° C and 60% humidity for 7 days,
An exposure test was performed using a Sunshine Super Long Life Weather Meter manufactured by Suga Test Instruments Co., Ltd., and the surface condition after 1000 hours was observed. The results are shown in Tables 1 to 4.

[0175]

[Table 1]

[0176]

[Table 2]

[0177]

[Table 3]

[0178]

[Table 4]

From Tables 1 to 4, Examples 3 to 8 and 1 using the polyoxyalkylene polymer as the graft polymer.
It can be seen that the polymer and curable composition of No. 1 have higher storage stability than the polymers and curable compositions of Comparative Examples 2 to 4 using the polyoxyalkylene polymer as the blend polymer. Further , the polymers and compositions of Examples 3 to 8 and 11 using the polyoxyalkylene polymer having a small molecular weight distribution Mw / Mn are Comparative Example 1 using the polyoxyalkylene polymer having a large molecular weight distribution Mw / Mn. It can be seen that the viscosity is lower than that of the polymer and the composition.

(Test 2) A method of polymerizing a polymerizable monomer in the presence of a polyoxyalkylene polymer, which is obtained by polymerizing in the presence of a polyoxyalkylene polymer having a different molecular weight distribution Mw / Mn. With respect to the polymers of Example 7 and Comparative Example 1 having the same monomer composition, curability was compared in the following manner.

In the same manner as in the evaluation of weather resistance, the curable composition filled in the sealing material cartridge was poured into a cylindrical (diameter 4 cm) cup so as to have a thickness of 4 cm, and then at 65 ° C. at 20 ° C. It was left in an atmosphere of% humidity for 6 hours. After that, using a penetration meter conforming to JIS K2530, a 1.25 g needle for asphalt was used to show the state of curing from the surface to the depth direction from the top to the bottom in the vertical direction for 5 seconds. It was measured as a degree (unit: cm). The higher the penetration, the less the hardening from the surface. The results are shown in Table 5.

[0182]

[Table 5]

From the results of Table 5, the molecular weight distribution M of Example 7
The curable composition using a polyoxyalkylene polymer having a w / Mn of 1.7 or less has a molecular weight distribution Mw / M of Comparative Example 1.
It can be seen that the viscosity is low and the curability is excellent as compared with the curable composition using the polyoxyalkylene polymer having n of 2.2.

(Test 3) The same polyoxyalkylene polymer as the polymer of Example 3 obtained by polymerizing the polymerizable monomer in the presence of the polyoxyalkylene polymer was used as the polymerizable monomer. The composition of Comparative Example 4 (monomer composition is the same) obtained by mixing with the polymer of Example 1 was subjected to a shear adhesion test in the following manner.

For each 100 parts of the polymer of Example 3 and the composition of Comparative Example 4, 2 parts of dibutyltin laurate,
A curable composition was obtained by blending 2 parts of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.

This curable composition was dried at 23 ° C. and 50% humidity to give a width of 25 mm, a length of 100 mm and a thickness of 3 mm.
On the aluminum plate of No. 1 to have an adhesion area of 25 mm × 25 mm and a thickness of about 0.2 mm, and after 30 seconds, another piece of aluminum plate is alternately stacked and adhered, and cured for 7 days under the same conditions. Tensile shear adhesive strength (kg /
cm ² , tensile speed: 5 mm / min) was measured. The results are shown in Table 6.

[0187]

[Table 6]

From the results shown in Table 6, the curable composition using the polymer of Example 3 grafted with the polyoxyalkylene polymer was compared with the curable composition using the composition of Comparative Example 4, It can be seen that the adhesive strength is improved.

[0189]

As described above, according to the present invention,
It is possible to obtain a polymer having a low viscosity and excellent handleability and storage stability. Further, by containing the polymer in the curable composition, a curable composition having excellent curability, mechanical properties of the cured product, and weather resistance can be obtained.

The curable composition of the present invention can be used as a sealant, a waterproof material, an adhesive, a coating agent, a caulking agent, a sizing agent, and the like. In particular, the curable composition itself has a sufficient cohesive force and a dynamic property to an adherend. It is suitable for applications where followability is required.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-161420 (JP, A) JP-A-6-172631 (JP, A) JP-A-5-65403 (JP, A) JP-A-7- 258535 (JP, A) JP-A-4-283258 (JP, A) JP-A-4-283259 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 290/00-290 / 14 C08L 55/00 C09J 155/00 C09K 3/10

Claims (7)

(57) [Claims] 1. A cyclic ether is polymerized in the presence of an initiator, using a complex metal cyanide complex as a catalyst, and the following 1) to
It has the characteristics of 3) and is further represented by the following general formula (1).
Contains 0.01 mmol / g or more of hydrolyzable silicon group
That after obtaining polyoxyalkylene polymer (A), the polyoxyalkylene polymer (A), at least one selected from acrylic acid alkyl esters and methacrylic acid alkyl ester monomer as a polymerizable monomer 2. The method for producing a polymer, which comprises polymerizing the monomer (B) or the monomer (B) with another polymerizable unsaturated group-containing monomer (C). 1) Molecular weight distribution Mw / Mn, which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), is 1.7 or less 2) Molecular weight 8,000 to 50,000 3) Main chain ends and / or side chains An unsaturated group of 0.01 m
mol / g or more containing the general ^{_{formula: -SiX a R 1 3-a}} ... (1) (R 1: Charcoal
Substituted or unsubstituted monovalent organic group having a prime number of 1 to 20, X: water
Acid group or hydrolyzable group, a: an integer of 1 to 3. However, R
When a plurality of ¹ 's are present, their R ^1s are the same or different.
May be. If there are multiple Xs,
The X's may be the same or different. ) 2. As the monomer (B), at least one monomer (D) selected from an alkyl acrylate and an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, and carbon The method for producing a polymer according to claim 1, wherein the polymer is used in combination with at least one monomer (E) selected from acrylic acid alkyl esters and methacrylic acid alkyl esters having several tens or more alkyl groups. 3. The other polymerizable unsaturated group-containing monomer (C) is essential as the polymerizable monomer, and the other polymerizable unsaturated group-containing monomer (C) is The method for producing a polymer according to claim 1, which comprises a hydrolyzable silicon group represented by the general formula (1). General ^{_{formula: -SiX a R 1 3-a}} ... (1) (R 1: a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X: hydroxyl group or a hydrolyzable group, a: 1 to 3 Integer.
However, when a plurality of R ¹ 's are present, those R ¹ 's may be the same or different. Further, when there are a plurality of Xs, the Xs may be the same or different. ) 4. The method of claim 1 and polymer obtained by the production method according to any one of 3, the curable composition comprising a curing acceleration catalyst. 5. Further, 0.1 or less of a hydrolyzable silicon group represented by the following general formula (1) is added to the terminal and / or side chain of the main chain.
The curable composition according to claim 4 , which comprises a polyoxyalkylene polymer (F) contained in an amount of mmol / g or more. General ^{_{formula: -SiX a R 1 3-a}} ... (1) (R 1: a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X: hydroxyl group or a hydrolyzable group, a: 1 to 3 Integer.
However, when a plurality of R ¹ 's are present, those R ¹ 's may be the same or different. Further, when there are a plurality of Xs, the Xs may be the same or different. ) 6. The polyoxyalkylene polymer (F)
But claim 5 are those having the following characteristics 1) to 2)
The curable composition according to. 1) The molecular weight distribution Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), is 1.7 or less. 2) The molecular weight is 8,000 to 50,000. 7. The polyoxyalkylene polymer (F)
7. The curable composition according to claim 6 , wherein is a derivative of a polymer obtained by polymerizing a cyclic ether with a double metal cyanide complex as a catalyst in the presence of an initiator.