JP2000136313A - Room temperature curable composition - Google Patents

Abstract

(57) [Problem] To provide a room temperature curable composition having excellent curability and surface weather resistance. A polymer (A) having a hydrolyzable silicon group in which three hydrolyzable groups are bonded to silicon as an essential component, and an air-curable compound (K) and / or a photo-curable compound (L). Room temperature curable composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a 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 a terminal is used for applications such as a coating composition and a sealing composition by making use of a characteristic that a cured product has rubber elasticity.

[0003]

The method of curing various polymers having a hydrolyzable silicon group at the terminal and using them in sealants, adhesives, etc. is well known and is an industrially useful method. . Among such polymers, particularly those having a main chain of polyoxyalkylene are liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and is used as a sealant, an adhesive or the like. Has favorable properties.

[0004] Such moisture-curable polymers include:
A polymer having a hydrolyzable silicon group at a terminal, which is described in JP-B-61-18852, JP-A-3-72527 and JP-A-3-47825. A polymer having a hydrolyzable silicon group in which two hydrolyzable groups are bonded to each other, and three hydrolyzable groups per silicon atom described in JP-B-58-10418 and JP-B-58-10430. There is known a polymer having a hydrolyzable silicon group formed by bonding a functional group and having a relatively low molecular weight of 6000 or less.

[0005] However, such a polymer is insufficient in curing speed, especially when an extremely fast curing speed is required, such as in an adhesive application or when used at a low temperature. If it is desired, the cross-linking density must be reduced, and therefore the cross-linking density is not sufficient, causing stickiness (surface tack), and the surface is liable to crack in the long term due to weather resistance deterioration. Was. To solve this problem, a method of adding a photo-curable compound or an air-curable compound is disclosed in
26349, JP-A-1-198661, JP-A-2-11
7954, JP-A-3-160053, JP-A-5-705
31, JP-A-5-65400, JP-A-5-65407,
Attempts have been made in JP-A-7-196909, JP-A-8-269315 and the like, and in particular, JP-A-5-65400 and JP-A-5-65407 describe examples in which a polymer having a narrow molecular weight distribution is used. However, these known examples are practically only examples of a monoalkyl dialkoxysilyl group as a curable functional group, and in such a case, it has been difficult to increase the curing rate.

[0006] As described above, there is a demand for a polymer having a hydrolyzable silicon group that can improve the curing property and the surface weather resistance very quickly without greatly deteriorating its flexibility and workability. Was.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a room-temperature curable composition having excellent curing characteristics and surface weather resistance by using a specific air-curable compound or photocurable compound. .

A polymer having a hydrolyzable silicon group represented by the following formula (1), wherein a part or all of the polymer has a hydrolyzable silicon group in which a of the formula (1) is 3 A room-temperature curable composition comprising, as essential components, a polymer (A) that is a polymer having the compound (A), an air-curable compound (K), and / or a photocurable compound (L).

[0009] ^{_{-SiX a R 1 3-a ···}} (1) ( in the formula (1), R ¹ is a monovalent organic group, substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable A radical, a
Represents 1, 2 or 3. However, when a plurality of R ¹ are present, those R ¹ may be the same or different, and X 1
When there are a plurality of, Xs thereof may be the same or different. )

(Polymer (A)) In the present invention, the main chain of the polymer (A) includes polyoxyalkylene, polyester, polycarbonate, polyolefin and the like. Is particularly preferred. Hereinafter, the polymer (A) having a main chain of polyoxyalkylene (hereinafter referred to as polyoxyalkylene polymer (B)) will be described as a representative.

(Polyoxyalkylene polymer (B)) The polyoxyalkylene polymer (B) having a hydrolyzable silicon group represented by the formula (1) is disclosed in, for example, JP-A-3-47.
825, JP-A-3-72527, JP-A-3-79627
And so on. As described below, the polyoxyalkylene polymer (B) is obtained by using a polyoxyalkylene polymer having a functional group as a raw material and introducing a hydrolyzable silicon group to the terminal thereof with or without an organic group. It is preferably manufactured.

The starting polyoxyalkylene polymer is preferably a hydroxyl-terminated polymer produced by reacting a cyclic ether or the like in the presence of a catalyst and an initiator. 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 composite 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 by using the same.

It is particularly preferred to use a polyoxyalkylene polymer having a weight average molecular weight (M _w ) and number average molecular weight (M _n ) ratio M _w / M _n of 1.7 or less,
M _w / M _n is more preferably 1.6 or less,
M _w / M _n is particularly preferably 1.5 or less.

The polyoxyalkylene polymer (B) having a hydrolyzable silicon group of the present invention can be obtained by further modifying the terminal group of such a polyoxyalkylene polymer as a raw material to obtain a hydrolyzable silicon group. Can be As the raw material polyoxyalkylene polymer _Mw / _Mn is smaller, when the polyoxyalkylene polymer (B) obtained by using it as a raw material is cured, even if the elastic modulus is the same, the cured product has larger elongation and higher strength. And the viscosity of the polymer is reduced, resulting in excellent workability. Among such polyoxyalkylene polymers, those obtained by polymerizing an alkylene oxide in the presence of an initiator particularly using a double metal cyanide complex as a catalyst are particularly preferable, and the terminal of such an alkylene oxide polymer is modified. It is most preferable to use a hydrolyzable silicon group.

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. In this case, as the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), or the like is preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As the alcohol, t-butanol is preferable.

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 characteristic, 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 from 3 to 8.

Specific examples of the raw material polyoxyalkylene polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, and copolymers of two or more cyclic ethers. Can be

Particularly preferred starting polyoxyalkylene polymers are polyoxypropylene polyols having 2 to 6 valences, particularly polyoxypropylene diol and polyoxypropylene triol. In addition, the following (a) and (d)
In the above method, an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monol can also be used.

The polyoxyalkylene polymer (B) is
It has a hydrolyzable silicon group represented by the following formula (1) at the terminal or side chain of the molecular chain. During ^{_{-SiX a R 1 3-a ···}} (1) ( Formula (1), R ¹ R ¹ is a monovalent organic group, substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group or hydrolytic Is a decomposable group, and a is 1, 2 or 3.
When a plurality of ¹ 's are present, R ¹ 's thereof may be the same or different, and when a plurality of X's exist, those X's may be the same or different. )

The hydrolyzable silicon group represented by the formula (1) is usually introduced into the raw material polyoxyalkylene polymer via an organic group. That is, the polyoxyalkylene polymer (B) preferably has a group represented by the formula (2). ^{_{-R 0 -SiX a R 1 3-}} a ··· (2) ( in the formula (2), R ⁰ is a divalent organic group, R ^1, X, a are as defined above.)

In the formulas (1) and (2), R ¹ has 1 to 20 carbon atoms.
Is a substituted or unsubstituted monovalent organic group, 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, a propyl group, a butyl group, a hexyl group. Group, cyclohexyl group, phenyl group and the like. When R 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 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. When a plurality of Xs exist, those Xs may be the same or different.

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

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

(A) A method in which an olefin 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 (3). ^{_{HSiX a R 1 3-a ···}} (3) ( in the formula ^{(3), R 1, X} , a are as defined above.)

As a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene polymer having a hydroxyl group to form an ether bond, an ester bond, a urethane bond or a carbonate bond. And the like. When polymerizing the alkylene oxide, a method of adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing the same to introduce an olefin group into the side chain of the raw material polyoxyalkylene polymer can also be used.

When reacting a 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 in which a compound represented by the formula (4) is reacted with a terminal of a polyoxyalkylene polymer having a hydroxyl group. ^{_{R 1 3-a -SiX a -R}} 2 in NCO ··· (4) (formula ^{(4), R 1, X} , a divalent hydrocarbon group having the same .R ² is 1 to 17 carbon atoms in the )) In the above reaction, a known urethanation catalyst may be used. The above reaction is 2
It is preferably carried out at a temperature of 0 to 200 ° C, preferably 50 to 150 ° C for several hours.

(C) A polyisocyanate compound such as tolylene diisocyanate is reacted with the terminal of the polyoxyalkylene polymer having a hydroxyl group to form an isocyanate group terminal, and the silicon compound represented by the formula (5) is added to the isocyanate group. Reacting the W group of ^{_{R 1 3-a -SiX a -R}} 2 W in (5) (Equation ^{(5), R 1, R} 2, X, a are as .W the hydroxyl group, a carboxyl group, a mercapto group and an amino Active hydrogen-containing group selected from groups (primary or secondary).)

(D) After introducing an olefin group to the terminal of the polyoxyalkylene polymer having a hydroxyl group, the olefin group is reacted with a mercapto group of a silicon compound represented by the formula (5) wherein W is a mercapto group. How to let.

Examples of the silicon compound represented by the formula (5) wherein W is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyl Triethoxysilane,
And the like.

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-2-methylbutyronitrile, benzoyl peroxide, t-alkylperoxyester, acetyl peroxide, and diisopropylperoxycarbonate. The above reaction is preferably carried out at 20 to 200 ° C, preferably 50 to 150 ° C, for several hours to several tens of hours.

(In the case where the main chain is other than a polyoxyalkylene polymer) When the main chain of the polymer (A) is a polyester or a polycarbonate, a polyoxyalkylene is used as a starting material from a hydroxyl-terminated polyester or a hydroxyl-terminated polycarbonate, respectively. It can be produced by the same production method as for the polymer (B).

When the main chain is a polyolefin, the polyoxyalkylene polymer (B) can be produced by using a hydroxyl-terminated polyolefin such as polybutadiene polyol or hydrogenated polybutadiene polyol as a raw material in the same manner as for the polyoxyalkylene polymer (B). Further, after isobutylene is polymerized by using 1,4-bis (1-chloro-1-methylethyl) benzene as an initiator and boron trichloride as a catalyst, a dehydrochlorination reaction is performed. It can be produced using the isobutylene-based polymer as a raw material by the same production method as for the polyoxyalkylene polymer (B).

(Hydrolysable Silicon Group wherein a in Formula (1) is 3) The polymer (A) of the present invention is partially or entirely composed of "hydrolyzable silicon group wherein a in Formula (1) is 3 Silicon group "
(Hereinafter referred to as “hydrolyzable silicon group (E)”).

As the “hydrolyzable silicon group (E)”,
A group in which X in the formula (1) is an alkoxy group having 4 or less carbon atoms, that is, a trialkoxysilyl group having an alkoxy group having 4 or less carbon atoms is particularly preferable. A polymer having a trialkoxysilyl group is very reactive, and particularly has a very fast initial curing rate.

Usually, in the hydrolysis reaction of the hydrolyzable silicon group represented by the formula (1), a silanol group is generated by the reaction with water (-SiX + H ₂ O → -SiO
It is considered that the reaction proceeds by a reaction (silanol group generation reaction represented by H + HX), and further, a generated silanol group is condensed or condensed 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 and a triethoxysilyl group are 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. Therefore,
The “hydrolyzable silicon group (E)” is most preferably a trimethoxysilyl group. Further, the polymer (A)
The ratio of the hydrolyzable silicon group (E) in the hydrolyzable silicon group represented by the formula (1) can be changed according to the use, required characteristics, and the like.

When the polymer (A) is a polymer having only the hydrolyzable silicon group (E) as the hydrolyzable silicon group, that is, represented by the formula (1) in the polymer (A). Nearly 100% of the hydrolyzable silicon groups (ie 8
When (0 to 100%) is a hydrolyzable silicon group (E), there is an effect that the curing speed is high, and a room temperature curable composition having particularly excellent curability leading to the development of adhesiveness can be obtained. In this case, it is preferable that 90 to 100%, particularly 95 to 100%, of the hydrolyzable silicon group (E) represented by the formula (1) is the hydrolyzable silicon group (E).

When the hydrolyzable silicon group in which a in the formula (1) is 1 or 2 and the hydrolyzable silicon group (E) are mixed, good elongation characteristics and rapid curability are obtained. A compatible room temperature curable composition is obtained.

In this case, the proportion of the hydrolyzable silicon group (E) in the total hydrolyzable silicon group represented by the formula (1) in the polymer (A) is preferably 5 to 80%. By changing this ratio arbitrarily, the characteristics according to the requirements can be freely controlled. That is, when the proportion of the hydrolyzable silicon group (E) is 5 to 50%, the curability can be improved and the good elongation characteristics and flexibility required for a sealant or the like can be provided. When the proportion of the hydrolyzable silicon group (E) is 50 to 80%, the elongation characteristics required for an elastic adhesive or the like can be sufficiently secured and the curability can be dramatically improved.

In the hydrolyzable silicon group represented by the formula (1), the hydrolyzable silicon group other than the hydrolyzable silicon group (E) is the hydrolyzable silicon group represented by the formula (1) wherein a is 2 Particularly preferred is a group. Particularly preferred is a dialkoxyalkylsilyl group having an alkoxy group having 4 or less carbon atoms. A dimethoxymethylsilyl group is most preferred.

A mixture of a hydrolyzable silicon group (E) and a hydrolyzable silicon group in which a in Formula (1) is 1 or 2
Methods for obtaining the polymer (A) include, for example, the following methods (e) and (f), and the methods (e) and (f) may be used in combination. (E) As the polymer (A), a polymer having both a hydrolyzable silicon group and a hydrolyzable silicon group (E) in which a in Formula (1) is 1 or 2 is used. (F) As the polymer (A), a polyoxyalkylene polymer (B) having a hydrolyzable silicon group wherein a in Formula (1) is 1 or 2 and a polymer having a hydrolyzable silicon group (E) Both coalescing (A) are used.

The molecular weight of the polymer (A) in the present invention is:
You can select an appropriate value depending on the application used,
The molecular weight of the polymer (A) is preferably from 8,000 to 50,000.

For applications such as sealants where flexibility is important, polymers having a molecular weight of 8,000 to 50,000 are preferred. The molecular weight is particularly preferably 8,000 to 25,000, and most preferably 12,000 to 20,000. For applications such as adhesives that require strength,
A polymer having a molecular weight of 8,000 to 30,000 is preferred. 80
If it is lower than 00, the cured product becomes brittle and becomes 30,000
If it exceeds, the workability becomes extremely poor due to the high viscosity.
The molecular weight is more preferably from 8,000 to 20,000, particularly preferably from 12,000 to 20,000.

(Polymer (D) Obtained by Polymerizing Polymerizable Unsaturated Group-Containing Monomer (C)) A room temperature curable composition containing the polymer (A) as an essential component has excellent curability. In the present invention, among the polymers (A), when the polyoxyalkylene polymer (B) is used, the polyoxyalkylene polymer (B) further comprises a polymerizable unsaturated group-containing monomer (C).
It is preferable to contain a polymer (D) obtained by polymerizing By containing the polymer (D), the effect of imparting adhesiveness in the initial stage of the curing reaction, that is, the effect of extremely shortening the time until the adhesive strength is exhibited, can be obtained.

Typical examples of the polymerizable unsaturated group-containing monomer (C) include, but are not limited to, compounds represented by the following formula (6). CRR ⁵ = CR ³ R ⁴ (6) (wherein, 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 has 1 carbon atom.
It is preferably a monovalent substituted or unsubstituted hydrocarbon group of 10 to 10. R and R ⁵ are more preferably each a hydrogen atom. The organic group in R ³ and R ⁴ has 1 carbon atom.
10 to 10 monovalent 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 glycidyl It is preferably an oxycarbonyl group. R ³ is a hydrogen atom, a halogen atom or a C 1 -C 1
Particularly preferred is 10 monovalent substituted or unsubstituted hydrocarbon groups.

Specific examples of the polymerizable unsaturated group-containing monomer (C) include styrene monomers such as styrene, α-methylstyrene and chlorostyrene; acrylic acid, methacrylic acid, methyl acrylate and methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate,
Acrylic monomers such as acrylic acid such as benzyl methacrylate, methacrylic acid or esters thereof, acrylamide and methacrylamide; acrylonitrile;
-A cyano group-containing monomer such as dicyanobutene-1; a vinyl ester monomer such as vinyl acetate and vinyl propionate; a diene monomer such as butadiene, isoprene and chloroprene; vinyl glycidyl ether, allyl glycidyl ether and meta- Glycidyl group-containing monomers such as ruly glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; and olefins, unsaturated esters, halogenated olefins, and vinyl ethers other than these.

As the polymerizable unsaturated group-containing monomer (C), one type may be used alone, or two or more types may be used in combination. When a cyano group-containing monomer, a glycidyl group-containing monomer or a styrene-based monomer is used, especially when acrylonitrile, glycidyl acrylate, glycidyl methacrylate or styrene is used, even better adhesive properties and mechanical properties are obtained. It is preferable because it can be expressed. In particular, when rubber elasticity is required after curing, it is preferable to use an acrylate ester.

As the polymerizable unsaturated group-containing monomer (C), a polymerizable monomer having a hydrolyzable silicon group represented by the formula (1) can be used. As such a polymerizable monomer having a hydrolyzable silicon group, a compound represented by the following formula (7) is particularly preferable. During ^{_{R 7 -SiY b R 6 3-}} b ··· (7) ( Equation ^(7), R 7 is a monovalent organic group having a polymerizable unsaturated group, R ⁶ is 1 to 20 carbon atoms A substituted or unsubstituted monovalent organic group, Y is a hydroxyl group or a hydrolyzable group, and b is 1, 2 or 3. However, when a plurality of R ⁶ are present, those R ⁶ are They may be the same or different, and when there are a plurality of Ys, those Ys may be the same or different.)

Examples of the polymerizable monomer having a hydrolyzable silicon group include a vinyl monomer having a hydrolyzable silicon group,
An acrylic monomer having a hydrolyzable silicon group is exemplified. Specific examples include the following, and 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane are particularly preferable.

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

In addition to these, for example, when a silicon atom is
Polysiloxane compounds having up to 30 compounds having both a carbon-carbon double bond and a silicon atom bonded to a hydrolyzable group can also be used as a polymerizable monomer having a hydrolyzable silicon group.

The polymerizable monomer having a hydrolyzable silicon group may be used alone or in combination of two or more. When a polymerizable monomer having a hydrolyzable silicon group is used, the monomer is preferably used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymerizable unsaturated group-containing monomer (C).

A part or all of the polymerizable unsaturated group-containing monomer (C) has a polymerizable unsaturated group and is glycidyl group and / or hydrolyzable silicon represented by the formula (1). It is preferably a monomer having a group.

(Polymer composition) When the polyoxyalkylene polymer (B) further contains a polymer (D), a polymer composition comprising the polyoxyalkylene polymer (B) and the polymer (D) The product can be manufactured by the following methods (g) to (g).

(G) Polyoxyalkylene polymer (B)
And a polymer (D) obtained by previously polymerizing the polymerizable unsaturated group-containing monomer (C). (H) A method of polymerizing a polymerizable unsaturated group-containing monomer (C) in a polyoxyalkylene polymer (B). (I) After polymerizing the polymerizable unsaturated group-containing monomer (C) in the unsaturated group-containing polyoxyalkylene polymer (F), the remaining unsaturated group in the polymer (F) To a hydrolyzable silicon group represented by the formula (1).
The conversion method is preferably a method in which the unsaturated group is reacted with the hydrosilyl compound represented by the formula (3). (N) A method of polymerizing a polymerizable unsaturated group-containing monomer (C) in a precursor of a polyoxyalkylene polymer (B), and then converting the precursor to a polyoxyalkylene polymer (B) . (L) After polymerizing the polymerizable unsaturated group-containing monomer (C) in the presence of a solvent or a diluent, it is mixed with the polyoxyalkylene polymer (B), and then, if necessary, the solvent or diluent. A method of distilling the agent.

The solvent is a polymerizable unsaturated group-containing monomer (C)
Can be selected as appropriate according to the type of. As the diluent, an unsaturated group-containing polyoxyalkylene polymer (F) is preferable.
During the polymerization, a polyoxyalkylene polymer (F) containing an unsaturated group may be present in a solvent or a diluent.

In the polymerization of the polymerizable unsaturated group-containing monomer (C), a polymerization initiator such as a radical generator may be used. In some cases, the polymerization is carried out by radiation or heat without using a polymerization initiator. May be. The polymerization initiator, the polymerization temperature, the polymerization time and the like are the same as described in the above (d).

When the polymer (D) is used in the present invention, the polymer (D) may be used in a weight ratio of the polyoxyalkylene polymer (B) / polymer (D) in the range of 100/1 to 1/300. preferable. 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 (D) may be uniformly dispersed in fine particles or may be uniformly dissolved in the polyoxyalkylene polymer (B). In consideration of the viscosity and workability of the composition, it is preferable that the composition is uniformly dispersed in fine particles.

In the present invention, an air-curable compound (K) and / or a photo-curable compound (L) are used together with the polymer (A). The use of the air-curable compound (K) is effective in improving the initial tack, and the use of the photo-curable compound (L) is effective in improving the stain resistance and crack suppression. It is particularly preferable to use the air-curable compound (K) and the photo-curable compound (L) together.

As the air-curable compound (K) used in the present invention, a compound having an unsaturated group in the molecule which is polymerized by oxygen in the air is preferable. In particular,
A drying oil, a modified drying oil, a liquid diene polymer or a modified oil of a liquid diene polymer is preferred.

Examples of the drying oil include tung oil, linseed oil, eno oil, soybean oil, sunflower oil, hemp oil and the like. As a modified product of the drying oil, various alkyd resins obtained by modifying the drying oil, a reaction product of the drying oil and the functional polyoxyalkylene, a reaction product of the drying oil and the isocyanate compound (urethane oil), An acrylic polymer modified with a drying oil, an epoxy resin modified with a drying oil, and a silicone resin modified with a drying oil may be used.

The liquid diene polymer and its modified products include butadiene, chloroprene, isoprene, 1,3
A liquid polymer obtained by homopolymerizing or copolymerizing a diene compound having 4 to 8 carbon atoms such as pentadiene, and a monomer such as acrylonitrile and styrene copolymerizable with the diene compound, which is mainly composed of a diene compound. Polymers such as NBR and SBR obtained by copolymerizing so as to obtain, and various modified products thereof (maleated modified product, boiled oil modified product, etc.).

Of these, drying oils, liquid diene polymers and modified liquid diene polymers are preferred. Drying oils are particularly preferred. The air-curable compound (K) may be used alone or in combination of two or more.

The effect may be enhanced by using a catalyst or a metal dryer which promotes the oxidation curing reaction together with the air-curable compound (K). Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt 2-ethylhexanoate, and zirconium 2-ethylhexanoate, and amine compounds.

The amount of the air-curable compound (K) used is 0.01 to 20 parts by weight based on 100 parts by weight of the polymer (A) or the total of the polymer (A) and the polymer (D). Is preferred. If the amount used is less than 0.01 part by weight, the effect of improving the initial tack as the purpose of using the air-curable compound (K) is insufficient, and if it exceeds 20 parts by weight, elongation of the cured product is impaired. The preferred amount is 1 to 10 parts by weight.

The photocurable compound (L) used in the present invention
The term “light” means that the molecular structure undergoes a chemical change in a very short time due to the action of light, thereby causing a physical property change such as curing.
Many compounds, such as monomers, oligomers, resins or compositions containing them, are known as such compounds.
Any commercially available one can be used. Typical examples thereof include unsaturated acrylic compounds, polyvinyl cinnamate, and azide resin, and unsaturated acrylic compounds are particularly preferable.

The unsaturated acrylic compound is preferably a monomer or oligomer having one or several acryloyl groups or methacryloyl groups, or a mixture thereof, and particularly preferably a compound having an acryloyl group. More specifically, a monomer such as di (meth) acrylate of a polyhydric alcohol or a molecular weight of 10,000 obtained by polymerizing the monomer.
The following oligoesters are preferred (the term “(meth) acrylate” refers to acrylate and methacrylate; the same applies hereinafter). Specific examples of polyhydric alcohol di (meth) acrylate include propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylol. And propane tri (meth) acrylate.

When the photocurable compound (L) is used, the amount of the polymer (A) or the polymer (A) and the polymer (D)
Is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight in total. If the amount is less than 0.01 part by weight, the improvement of the stain resistance, which is the purpose of using the photocurable compound (L), is insufficient, and if it exceeds 20 parts by weight, elongation of the cured product is impaired. The preferred amount is 1 to 10 parts by weight.

(Room Temperature Curable Composition) The room temperature curable composition of the present invention can contain the following additives. Hereinafter, the additives will be described.

(Filler) As the filler, known fillers can be used. The amount of the filler used is preferably 0.001 to 1000 parts by weight, particularly preferably 50 to 250 parts by weight, per 100 parts by weight of the polymer (A) or the total of the polymer (A) and the polymer (D). The following are specific examples of the filler. These fillers may be used alone or in combination of two or more.

Calcium carbonate whose surface is treated with a fatty acid or a resin acid-based organic substance, colloidal calcium carbonate having an average particle size of 1 μm or less, which is further pulverized;
Light calcium carbonate having an average particle diameter of 1 to 3 μm, calcium carbonate such as heavy calcium carbonate having an average particle diameter of 1 to 20 μm, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon produced by the sedimentation method 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 chip, mica , Powdered fillers such as 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.

(Plasticizer) As the plasticizer, known plasticizers can be used. The amount of the plasticizer is preferably 0.001 to 1000 parts by weight based on 100 parts by weight of the polymer (A) or the total of the polymer (A) and the polymer (D). The following are specific examples of the plasticizer.

Dioctyl phthalate, dibutyl phthalate,
Phthalate esters such as butylbenzyl phthalate. Aliphatic carboxylic acid esters such as dioctyl adipate, bis (2-methylnonyl) succinate, dibutyl sebacate and butyl oleate; Alcohol esters such as pentaerythritol ester. Trioctyl phosphate,
Phosphate esters such as 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. Polyethers such as polyoxypropylene glycol and derivatives thereof, poly-α-methylstyrene,
Polymer plasticizers such as styrene oligomers such as polystyrene, oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, and epoxidized polybutadiene.

(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 of them
Species or two or more are used. The curing accelerating catalyst is polymer (A) or a total of polymer (A) and polymer (D) of 100
It is preferable to use 0.001 to 10 parts by weight based on parts by weight.

Metal salts such as alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate, acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid, butylamine, hexylamine, octyl Amine, decylamine, aliphatic monoamines such as laurylamine, ethylenediamine, aliphatic diamines such as hexanediamine, diethylenetriamine, triethylenetetramine, aliphatic polyamines such as tetraethylenepentamine, piperidine, heterocyclic amines such as piperazine, Amine compounds such as aromatic amines such as metaphenylenediamine, ethanolamines, triethylamine, and various modified amines used as curing agents for epoxy resins. A mixture of a divalent tin compound such as tin 2-ethylhexanoate, tin naphthenate and tin stearate with the above amines.

Dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate and the following carboxylic acid type organotin compounds and mixtures of these carboxylic acid type organic tin compounds with the above amines. (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 = CH
COOCH ₃ ) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (OCOCH =
CHCOOC ₄ H ₉ -n) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (O
_{COCH = 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 S
_{n (SCH 2 COO), (} n-C 8 H 17) 2 Sn (SCH
_{2 CH 2 COO), (n} -C 8 H 17) 2 Sn (SCH 2 C
_{OOCH 2 CH 2 OCOCH 2 S)} , (n-C 4 H 9) 2
_{Sn (SCH 2 COOC 8 H 17} -iso) 2, (n-C 8
_{H 17) 2 Sn (SCH 2} COOC 8 H 17 -iso) 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} organic such as SnO tin oxide, and reaction products of these organic tin oxide and an ester compound.
Examples of the ester compound include ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, and dioctyl phthalate.

The following chelate tin compounds and the reaction products of these tin compounds with alkoxysilanes (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).

The following tin compounds: _{(N-C 4 H 9)} 2 (CH
_{3 COO) SnOSn (OCOCH 3)} (C 4 H 9 -
_{n) 2, (n-C} 4 H 9) 2 (CH 3 O) SnOSn (OCH
_{3) (C 4 H 9 -n} ) 2.

(Adhesiveness-imparting agent) An adhesiveness-imparting agent is used for the purpose of further improving adhesiveness. Examples of these adhesiveness-imparting agents include silane coupling agents such as (meth) acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes. .

Examples of the (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-aminopropyltrimethoxy Silane, 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.

Examples of epoxy group-containing silanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

The carboxyl group-containing silanes include 2
-Carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, N- (N-carboxylmethyl-2-aminoethyl) -3-aminopropyltrimethoxysilane and the like.

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 silanes and mercapto group-containing silanes.
These reactants can be easily obtained by mixing the silane coupling agent and stirring at a temperature in the range of room temperature to 150 ° 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 polymer (A) or the polymer (A) and the polymer (D).
Is preferably 0 to 30 parts by weight with respect to 100 parts by weight in total.

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 10% of the total of the polymer (A) or the polymer (A) and the polymer (D).
0 to 100 parts by weight relative to 0 parts by weight is preferred.

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-
Commonly used epoxy resins such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerin, hydantoin type epoxy resin, 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, 2,4,4
Amines such as 6-tris (dimethylaminomethyl) phenol or salts thereof, or blocked amines such as ketimine compounds, polyamide resins, imidazoles, dicyandiamides, boron trifluoride complex compounds, phthalic anhydride, hexa Hydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride,
A polyalkylene oxide-based polymer having at least one group capable of reacting with a carboxylic acid anhydride such as pyromellitic anhydride, a phenoxy resin, a carboxylic acid, an alcohol, or an epoxy group in the molecule (terminally aminated poly) Oxypropylene glycol, terminal carboxylated polyoxypropylene glycol, etc.), liquid terminal functionalities such as polybutadiene, hydrogenated polybutadiene, acrylonitrile-butadiene copolymer, acrylic polymer, etc., whose terminals are modified with hydroxyl group, carboxyl group, amino group, etc. Group-containing polymers and the like.

(Solvent) When the composition of the present invention is used as a curable composition, a solvent may be added for the purpose of adjusting the viscosity and improving the storage stability of the composition. The solvent is used in an amount of 0.001 to 500 parts by weight per 100 parts by weight of the polymer (A) or the total of the polymer (A) and the polymer (D).
Parts by weight are preferred.

As the solvent, 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.

(Dehydrating Agent) In order to further improve the storage stability of the curable composition of the present invention, a small amount of a dehydrating agent can be added as long as the curability and flexibility are not adversely affected. The amount of the dehydrating agent used is 0.001 to 3 with respect to 100 parts by weight of the polymer (A) or the total of the polymer (A) and the polymer (D).
0 parts by weight is preferred.

Specifically, alkyl orthoformates such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetates such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane A hydrolyzable organic silicon compound such as silane, a hydrolyzable organic titanium compound, or the like can be used. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in terms of cost and effect.

(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.

(Anti-aging agent) Examples of the anti-aging agent include antioxidants, ultraviolet absorbers and the like which are generally used.
Light stabilizers are used as appropriate. Hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, and sulfur compounds can be used as appropriate.

(Others) Examples of the pigment include inorganic pigments such as iron oxide, chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green.

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

[0107]

EXAMPLES The polymers (P1 to P1) produced in Production Examples 1 to 23 were prepared.
Examples and comparative examples in which a cured product was produced using 23) are shown below. In addition, a part shows a weight part. Production Example 1
In 13, the term "hydroxyl equivalent molecular weight" refers to a molecular weight calculated from the hydroxyl value of a polyoxyalkylene polymer having a hydroxyl group as a raw material. M _w / M _n is a value measured by gel permeation chromatography using tetrahydrofuran as a solvent. The calibration curve was created using polyoxyalkylene polyol. Production Examples 14-1
In 7, the molecular weight was measured by gel permeation chromatography using tetrahydrofuran as a solvent. The calibration curve was created using polystyrene.

(Production Example 1) Propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. A methanol solution of sodium methoxide was added to polypropylene oxide having a hydroxyl value-converted molecular weight of 17000 and M _w / M _n = 1.3, and methanol was distilled off under reduced pressure under heating to convert the terminal hydroxyl group of the polypropylene oxide into sodium alkoxide. . Next, allyl chloride was reacted. The unreacted allyl chloride was removed and purified to obtain an allyl group-terminated polypropylene oxide (this is referred to as polymer U1). When the remaining hydroxyl groups were analyzed by a method for measuring a hydroxyl value, it was 0.01 mmol / g. The polymer U1 was reacted with trimethoxysilane which is a hydrosilyl compound in the presence of a platinum catalyst to obtain a polymer P1 having an average of two trimethoxysilyl groups at terminals.

(Production Example 2) A propylene oxide is reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst using propylene glycol as an initiator, and has a hydroxyl value-converted molecular weight of 17000 and M _w / M _n = 1.3.
Was used to obtain a polypropylene oxide having an allyl group at the terminal (the remaining hydroxyl group was 0.01 mmol / g) in the same manner as in Production Example 1. The reaction product was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P2 having an average of 1.3 terminal trimethoxysilyl groups.

(Production Example 3) A hydroxyl value-converted molecular weight of 15,000 and _Mw / _Mn = 1.3, obtained by reacting propylene oxide with sorbitol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Using polypropylene oxide, a polypropylene oxide having an allyl group at the end was obtained in the same manner as in Production Example 1 (remaining hydroxyl group: 0.01 mmol / g). The reaction product was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P3 having an average of 3.9 trimethoxysilyl groups at terminals.

(Production Example 4) Polymer U produced in Production Example 1
1, the molar ratio of methyldimethoxysilane, which is a hydrosilyl compound, to trimethoxysilane is 30: 7.
The mixture mixed at a ratio of 0 was reacted in the presence of a platinum catalyst to obtain a polymer P4 having an average of 0.6 methyldimethoxysilyl groups and an average of 1.4 trimethoxysilyl groups at the terminals.

(Production Example 5) Polymer U produced in Production Example 1
In response to 1, 3-mercaptopropyltrimethoxysilane as a silyl compound was reacted using 2,2′-azobis-2-methylbutyronitrile as a polymerization initiator,
A polymer P5 having an average of two trimethoxysilyl groups at the terminals was obtained.

(Production Example 6) Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to give a hydroxyl value-converted molecular weight of 17000.
After obtaining polyoxypropylene triol having M _w / M _n = 1.3, purification was carried out. Isocyanatepropyltrimethoxysilane was added thereto, and a urethanation reaction was carried out to convert both terminals into trimethoxysilyl groups.
Thus, a polymer P6 having a molecular weight of 18,000 and having trimethoxysilyl groups was obtained.

(Production Example 7) Polymer U produced in Production Example 1
1 was reacted with methyldimethoxysilane as a hydrosilyl compound in the presence of a platinum catalyst to obtain a polymer P7 having an average of two methyldimethoxysilyl groups at the terminals.

(Production Example 8) The same procedure as in Production Example 7 was carried out except that methyldiethoxysilane was used instead of methyldimethoxysilane as the hydrosilyl compound in Production Example 7, and an average of two terminals were used instead of the polymer P7. A polymer P8 having a methyldiethoxysilyl group was obtained.

(Production Example 9) A hydroxyl value-converted molecular weight of 7000 obtained by reacting propylene oxide with propylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst, and M _w / M _n = 1.2 Was used to obtain a polypropylene oxide having an allyl group at the terminal (the remaining hydroxyl group was 0.01 mmol / g) in the same manner as in Production Example 1. This reaction product was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst, and an average of 1.3 was obtained at the terminal.
A polymer P9 having three methyldimethoxysilyl groups was obtained.

(Production Example 10) A hydroxyl value-converted molecular weight of 7000 obtained by reacting propylene oxide with propylene glycol in the presence of a zinc hexacyanocobaltate-glyme complex catalyst and M _w / M _n = 1.2.
Was used to obtain a polypropylene oxide having an allyl group at the terminal (the remaining hydroxyl group was 0.01 mmol / g) in the same manner as in Production Example 1. This reaction product was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P10 having an average of 1.3 terminal trimethoxysilyl groups.

(Production Example 11) A methanol solution of sodium methoxide was added to polyoxypropylene diol having a molecular weight of 3,000 in terms of hydroxyl value obtained using a potassium hydroxide catalyst, and methanol was distilled off under reduced pressure under heating to remove the terminal hydroxyl group. Was converted to a sodium alkoxide. Next, after reaction with chlorobromomethane to increase the molecular weight, subsequently, allyl chloride was reacted. Unreacted allyl chloride was removed and purified to obtain a polypropylene oxide having an allyloxy group at the terminal (M _w / M _n = 1.9) (the remaining hydroxyl group was 0.01 mmol / g). This was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P11 having a molecular weight of 7000 and having an average of 1.3 trimethoxysilyl groups at terminals.

(Production Example 12) A hydroxyl value-converted molecular weight of 6,000, obtained using a potassium hydroxide catalyst, and M _w / M _n
= 1.9, a polypropylene oxide having an allyloxy group at the end was obtained in the same manner as in Production Example 1 (the remaining hydroxyl group was 0.0
1 mmol / g). This was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer P12 having an average of 1.3 trimethoxysilyl groups at terminals.

(Production Example 13) The polymer U1 produced in Production Example 1 was reacted with triethoxysilane which is a hydrosilyl compound in the presence of a platinum catalyst to give a polymer having an average of two triethoxysilyl groups at the terminals. P13 was obtained.

(Examples 1 to 20 and Comparative Examples 1 to 4) Among the polymers P1 to P13, the polymers 100 shown in Tables 1 to 3
Parts, 100 parts of fatty acid surface-treated calcium carbonate, 50 parts of heavy calcium carbonate, and 50 parts of a plasticizer shown in Tables 1 to 3.
Parts or 0 part, 3 parts of a thixotropy imparting agent, 1 part each of an ultraviolet absorber, a hindered amine light stabilizer and an antioxidant shown in Tables 1 to 3, 5 parts of an air-curable compound, and light shown in Tables 1 to 3 3 parts of a curable compound, 2 parts of 2-ethylhexanetin and 0.7 part of laurylamine as a curing catalyst previously mixed or 2 parts of dibutyltin bisacetylacetonate are added and uniformly mixed to form a curable composition. I got

For evaluating the internal curability of this composition, the time required for the composition viscosity to reach 1.6 million cps at 20 ° C. and 65% humidity was measured. Further, the kneaded composition is heated at 20 ° C.
The sheet was cured at 65% humidity for 7 days and at 50 ° C. and 60% humidity for 7 days to obtain a sheet having a thickness of 5 mm. The surface weather resistance of the sheet after 250 hours, 500 hours, and 750 hours was examined with a sunshine weatherometer. The evaluation was evaluated as ○ when no surface crack was observed after the sunshine weatherometer test, Δ when hair crack was observed, and × when clearly crack was observed. The results are shown in Tables 1 to 3.

(Terminal group of polymer) TM: trimethylsilyl group, DM: methyldimethoxysilyl group, TE: triethoxysilyl group, DE: methyldimethoxysilyl group.

(Air curable compound) A: Tung oil, B: Polymerized tung oil (China Tung No. 4), C: Urethane oil (UO-5), D: Linseed oil-modified alkyd (HL)
-20) (A to D: Tomen Chemical Co., Ltd.), E: liquid polybutadiene R-15HT (Idemitsu Petrochemical Co., Ltd.)
Made).

(Photocurable compounds) A: Alonix M309, B: M400, C: M806
0 (AC: manufactured by Toagosei Co., Ltd.), D: KAYARAD
(Manufactured by Nippon Kayaku Co., Ltd.), E: fluoroalkyl acrylate (C ₈ F ₁₇ C ₂ H ₄ ) ester, F: fluoroalkyl acrylate (C ₈ F ₁₇ C ₃ H ₆ ) ester (E, F:
(Asahi Glass Co., Ltd.).

(Ultraviolet absorber) A: Tinuvin 3277, B: Tinuvin 213 (A, B:
Ciba Specialty Chemicals).

(Hindered amine light stabilizer) A: Adekastab LA-52, B: Adekastab LA-
62, C: Adekastab LA-67, D: Adekastab LA63P (A to D: manufactured by Asahi Denka Kogyo KK), E: Tinuvin 144, F: Tinuvin 765, G: CHIMASS
OPB119FL (EG: Ciba Specialty Chemicals), H: Sanol LS765 (H: Sankyo Co., Ltd.).

(Antioxidants) A: Styrenated phenol (Nocrack SP, Ouchi Shinko Chemical), B: 2,6-di-t-butyl-4-methylphenol, C: Irganox 245 (B, C: Ciba Specialty Chemicals).

(Plasticizer) A: di (2-ethylhexyl) phthalate, B: molecular weight 1
0000 polyoxypropylene glycol-terminated allyl ether, C: di (2-ethylhexyl) 4,5-epoxycyclohexanedicarboxylate.

(Curing catalyst) A: A mixture of tin octylate and laurylamine, B: Dibutyltin bisacetylacetonate.

(Production Example 14) Based on the method described in JP-A-1-170681, 1,4-bis (1-chloro-1
Isobutylene is produced by polymerizing isobutylene using -methylethyl) benzene as an initiator and boron trichloride as a catalyst and then dehydrochlorinating and having an isopropenyl group at both ends at a ratio of about 92% and a molecular weight of about 5000. Trichlorosilane is combined with chloroplatinic acid as a catalyst at 90 ° C. 12
The reaction was continued for a time, and methyl orthoformate was further reacted with methanol to obtain a polyisobutylene-based polymer P14 having an average of 1.2 trimethoxysilyl groups at terminals.

(Production Example 15) Based on the method described in JP-A-1-170681, 1,4-bis (1-chloro-1
Isobutylene is produced by polymerizing isobutylene using -methylethyl) benzene as an initiator and boron trichloride as a catalyst and then dehydrochlorinating and having an isopropenyl group at both ends at a ratio of about 92% and a molecular weight of about 5000. 90 ° C of methyldichlorosilane with chloroplatinic acid as catalyst
12 hours, and further reacting methyl orthoformate and methanol to obtain a polyisobutylene-based polymer P having an average of 1.2 methyldimethoxysilyl groups at the terminals.
15 was obtained.

(Production Example 16) Hydrogenated polybutadiene having a hydroxyl group at a terminal (Polytail HA, manufactured by Mitsubishi Chemical Corporation)
Was reacted with 90 mol% of 3-isocyanatopropyltrimethoxysilane with respect to the terminal hydroxyl groups to obtain a hydrogenated polybutadiene polymer P16 having an average of 1.3 trimethoxysilyl groups at the terminals.

(Production Example 17) Hydrogenated polybutadiene having a hydroxyl group at a terminal (Polytail HA, manufactured by Mitsubishi Chemical Corporation)
Was reacted with 90 mol% of 3-isocyanatopropylmethyldimethoxysilane to obtain a hydrogenated polybutadiene polymer P17 having an average of 1.3 methyldimethoxysilyl groups at the terminals.

(Examples 21 to 27 and Comparative Examples 5 to 7)
Among polymers P14 to P17, polymer 1 shown in Tables 4 and 5
For 100 parts, 100 parts of colloidal calcium carbonate, 40 parts of heavy calcium carbonate, 65 parts of a hydrocarbon-based high boiling solvent (Hisol, Nippon Petrochemical Co., Ltd.), 5 parts of sodium sulfate hydrate, 1 part of anti-sagging agent And 5 parts of an air-curable compound, 3 parts of a photo-curable compound, 1 part of an ultraviolet absorber, 1 part of a hindered amine light stabilizer, and 1 part of an antioxidant.
A mixture of 2 parts of tin octylate and 0.7 part of laurylamine or 2 parts of dibutyltin bisacetylacetonate was mixed to obtain a curable composition.

The same test as in Examples 1 to 20 was performed on this composition. The results are shown in Tables 4 and 5.

(Production Example 18) 100 g of the polymer P1 was placed in a reactor equipped with a stirrer and heated to 100 ° C., to which 15 g of acrylonitrile and 15 g of styrene were dropped from a dropping funnel.
g and 2,2'-azobisisobutyronitrile 0.3
g solution was added over 3 hours with stirring. After further heating and stirring at 100 ° C. for 2 hours, deaeration was performed under reduced pressure to obtain a cloudy polymer mixture P18.

(Production Example 20) 50 g of the polymer P1 and 50 g of the polymer P7 were placed in a reactor equipped with a stirrer, and diluted with 50 g of toluene. The mixture was heated to 100 ° C. and acrylonitrile 20 g, styrene 20 g, glycidyl methacrylate 5 g, and 3-methacryloyloxypropyltrimethoxysilane 2 g were added to 2,2′-
A solution of 0 and 3 g of azobisisobutyronitrile was added dropwise with stirring over 3 hours. After dropping,
After a toluene solution of 0 and 2 g of 2′-azobisisobutyronitrile was added dropwise over 30 minutes, the mixture was heated and stirred at 100 ° C. for 3 hours. Toluene was distilled off from the obtained mixture at 100 ° C. under reduced pressure to obtain a cloudy polymer mixture P20.

(Production Example 22) 100 g of the polymer P13 was placed in a reactor equipped with a stirrer. This was heated to 100 ° C., and styrene 5 g, methyl methacrylate 10 g, butyl methacrylate 7 g, octadecyl methacrylate 2 g, 3 g
-Methacryloyloxypropyltrimethoxysilane 1
8 g, 2,2′-azobisisobutyronitrile 0.5 g
Was added dropwise over 3 hours with stirring. After completion of the dropwise addition, 2,2'-azobisisobutyronitrile was added to the mixture at 0.1.
After dropping 2 g of toluene solution over 30 minutes, 100
The mixture was heated and stirred at ℃ for 3 hours. 100 ° C from the resulting mixture
The toluene was distilled off under reduced pressure to obtain a cloudy polymer mixture P.
22 was obtained.

(Production Example 23) A polymer P23 was produced in the same manner as in Production Example 22 except that the polymer P8 (terminal of methyldiethoxysilyl group) was used instead of the polymer P13 as a raw material.
Was manufactured.

(Examples 28 to 34 and Comparative Examples 8 to 1)
0) Among the polymers P18 to P23, 100 parts of colloidal calcium carbonate, 40 parts of heavy calcium carbonate, 30 parts or 0 part of a plasticizer, and sodium sulfate hydrate 5 per 100 parts of the polymer shown in Tables 6 and 7 1 part, an anti-sagging agent, 5 parts of an air-curable compound, 3 parts of a photo-curable compound, 1 part of an ultraviolet absorber, 1 part of a hindered amine light stabilizer and 1 part of an antioxidant, and further, tin octylate 2 parts and laurylamine 0.
7 parts of the mixture or 2 parts of dibutyltin bisacetylacetonate was mixed to obtain a curable composition. The same test as in Examples 1 to 20 was performed on this composition. The results are shown in Tables 6 and 7.

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

[Table 3]

[0145]

[Table 4]

[0146]

[Table 5]

[0147]

[Table 6]

[0148]

[Table 7]

[0149]

The curable composition at room temperature of the present invention has an effect of being extremely excellent in curability and surface weather resistance.

Continuing from the front page (72) Inventor Tomomi Hayashi 1150 Hazawacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. CD202 CF171 CG021 CH051 CH052 CK022 CP032 CP131 CP181 EG046 EG076 EH070 EN006 FD010 FD020 FD030 FD090 FD150 FD156 FD340 GH00 GJ01 GJ02

Claims (12)

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