JP2003206410A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable composition which ensures practical curability and recovery properties and provides a cured material exhibiting mechanical properties with high strength and high elongation. <P>SOLUTION: This curable composition comprises (A) an organic polymer having a silicon-bonded hydroxy or hydrolyzable group and at least one silicon- containing group which can be crosslinked by the formation of a siloxane bond and one or more kinds of carboxylic acid metal salts selected (B) from calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate and zirconium carboxylate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond (hereinafter, referred to as
It is called "reactive silicon group". And a curable composition containing an organic polymer having

[0002]

2. Description of the Related Art An organic polymer containing at least one reactive silicon group in a molecule is crosslinked by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture even at room temperature, It is known to have an interesting property that a rubber-like cured product is obtained.

Among these polymers having a reactive silicon group, polyoxyalkylene polymers and polyisobutylene polymers are disclosed in JP-A-52-73998 and JP-A-5-1993.
-125272, JP-A-3-72527,
JP-A-63-6003, JP-A-63-6041, JP-A-1-38407, and JP-A-8-231.
No. 758, etc., and in particular, polyoxyalkylene-based polymers and polyisobutylene-based polymers are
Already industrially produced, it is widely used in applications such as sealants, adhesives and paints.

In particular, when the organic polymer is a saturated hydrocarbon polymer, the resulting cured product is excellent in heat resistance, water resistance, weather resistance and the like, and therefore is used as a sealing material for construction or a sealing material for double glazing. And is effective. Furthermore, an isobutylene-based polymer having a total amount of repeating units derived from isobutylene of 50% by weight or more is excellent in low moisture permeability and low gas permeability, and is therefore particularly suitable as a sealing material for the purpose of preventing moisture.

Since such a sealing material is generally used for the purpose of filling water-tightness and air-tightness by filling the joints and gaps between various members, it is extremely easy to follow the use site for a long period of time. It becomes important and it is required to develop sufficient elongation and strength.

On the other hand, a silanol condensation catalyst is used for crosslinking and curing such an organic polymer having a reactive silicon group, and an amine compound such as laurylamine is also used as a cocatalyst for the purpose of accelerating the condensation reaction. I often do it. As such silanol condensation catalysts, tin-based catalysts such as tin octylate (2-ethylhexanoate) tin and tetravalent tin such as dibutyltin bisacetylacetonate are widely used. When the movement of the portion where the sealing material is placed is large, etc., divalent tin is often used because a cured product having a restoring property can be obtained.

However, when, for example, tin octylate, which is divalent tin, is used as the component (A) curing catalyst in combination with the cocatalyst amine compound, the strength and elongation of the resulting cured product are insufficient. In some cases, further improvement in physical properties is desired.

Most of the latter tetravalent tin-based catalysts currently used are of the dibutyltin type, but the resulting cured product is relaxed, that is, it follows a long-term stress change from the outside. It is widely used because it has properties and has a fast curing property and can be applied as a curing catalyst for a one-pack type curable composition. However, since the toxicity of tributyltin contained in a small amount in this is problematic, development of a non-tin silanol condensation catalyst is desired.

Japanese Patent Publication No. 35-2795, Japanese Patent Publication No. 32
In Japanese Patent Publication No. 3742, Japanese Patent Publication No. 35-9639, Japanese Patent Publication No. 37-3271, etc., various non-tin carboxylic acid metal salts together with tin carboxylic acid salts are used as curing catalysts for organopolysiloxane compositions. Is disclosed. On the other hand, as an example in which a non-tin carboxylic acid metal salt is used as a curing catalyst for a composition containing an organic polymer having a reactive silicon group, bismuth carboxylate (JP-A-5-39428, JP-A-9-39428, -12860) and cerium carboxylate (Japanese Patent Laid-Open No. 2000-31381).
No. 4, but there has been no example in which various carboxylic acid metal salts have been widely studied.

[0010]

DISCLOSURE OF THE INVENTION In the present invention, particularly high durability is required because practical curability, the obtained cured product has good restorability and exhibits excellent strength and elongation. Sealing material for construction, sealing material for double glazing, moisture-proof sealing material used for electric and electronic parts,
An object is to provide a curable composition useful as an adhesive or the like.

[0011]

Means for Solving the Problems As a result of studies to solve such problems, the present inventors have found that as a curing catalyst for component (A), calcium carboxylate, vanadium carboxylate, iron carboxylate, carboxylic acid By using at least one metal carboxylate selected from titanium, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate, and zirconium carboxylate, it is possible to obtain appropriate curability and restoration property. The inventors have found that, while ensuring the properties, they exhibit physical properties of higher strength and higher elongation than when tin octylate is used as a curing catalyst, and have completed the present invention.

That is, the present invention provides (A) an organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond, B) at least one carboxylic acid selected from calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate, zirconium carboxylate The present invention relates to a curable composition containing a metal salt.

Further, it relates to the above-mentioned curable composition containing an amine compound as an essential component as the component (C).

In a preferred embodiment, the organic polymer as the component (A) has a number average molecular weight in the range of 500 to 50,000, and has the general formula (1) at the terminal and / or side chain of the main chain. :

[0015]

[Chemical 2] (In the formula, R ¹ and R ² each independently have 1 to 1 carbon atoms.
20 alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms (R ') ₃ SiO-
(R's are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), which is a triorganosiloxy group. Further, X is independently a hydroxyl group or a hydrolyzable group. Furthermore, a is 0, 1,
It is either 2, 3, b is 0, 1, 2, and a and b are never 0 at the same time. Also, m
Is 0 or an integer of 1 to 19) per molecule has one or more hydrolyzable silyl groups, the curable composition according to any one of the above.

[0016] In a further preferred embodiment, the above curable composition is characterized in that X is an alkoxy group.

As a further preferred embodiment, the curable composition according to any one of the above, wherein the organic polymer as the component (A) is a polyoxyalkylene polymer and / or a saturated hydrocarbon polymer.

In a further preferred embodiment, the curable composition is a saturated hydrocarbon polymer, which is a polymer characterized in that the total amount of repeating units derived from isobutylene is 50% by weight or more.

In a more preferred embodiment, the component (B) is calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate. The zirconium carboxylate relates to the curable composition according to any one of the above, wherein the zirconium carboxylate is mainly composed of the metal carboxylate represented by the general formulas (2) to (12). Ca (OCOR) ₂ (2) V (OCOR) ₃ (3) Fe (OCOR) ₂ (4) Fe (OCOR) ₃ (5) Ti (OCOR) ₄ (6) K (OCOR) (7) Ba (OCOR) ) ₂ (8) Mn (OCOR) ₂ (9) Ni (OCOR) ₂ (10) Co (OCOR) ₂ (11) Zr (O) (OCOR) ₂ (12) (wherein R is substituted or unsubstituted) It is a hydrocarbon group and may contain a carbon-carbon double bond.) In a further preferred embodiment, the carboxylic acid metal salt of the component (B) is an acid group of a carboxylic acid having a melting point of 65 ° C. or lower. The curable composition according to any one of the above, which is a carboxylic acid metal salt having.

In a more preferred embodiment, the carboxylic acid metal salt of the component (B) is a carboxylic acid metal salt having an acid group of a carboxylic acid having a carbon number of 2 to 17 containing a carbonyl group carbon. The curable composition according to claim 1.

In a further preferred embodiment, the component (B) metal carboxylic acid salt is a metal salt of a carboxylic acid group-containing compound selected from octyl acid, 2-ethylhexanoic acid, neodecanoic acid, oleic acid, or naphthenic acid. The curable composition according to any one of the above.

In a further preferred embodiment, the amount of the component (B) is 0.005 to 5 parts by weight in terms of the metal element contained in the component (B) with respect to 100 parts by weight of the component (A). The curable composition according to any one of the above, wherein the curable composition is contained.

In a further preferred embodiment, the amount of the component (B) is 0.005 to 5 parts by weight in terms of the metal element contained in the component (B), relative to 100 parts by weight of the component (A), (C) The curable composition according to any one of the above, which contains 0.01 to 20 parts by weight of the component.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The main chain skeleton of the organic polymer having a reactive silicon group used in the present invention is not particularly limited, and those having various main chain skeletons can be used.

Specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, polyoxypropylene-polyoxybutylene copolymers and the like Oxyalkylene polymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, etc., polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene Or a hydrocarbon-based polymer such as a hydrogenated polyolefin-based polymer obtained by hydrogenating these polyolefin-based polymers; condensation of a dibasic acid such as adipic acid and glycol, or ring-opening polymerization of lactones Obtained po Ester polymers; ethyl acrylate, polyacrylic acid ester monomer obtained by radical polymerization such as butyl acrylate, ethyl acrylate, acrylic acid esters and vinyl acetate and butyl acrylate, acrylonitrile, methyl methacrylate,
Vinyl-based polymers such as acrylic acid ester-based copolymers with styrene and the like; graft polymers obtained by polymerizing vinyl monomers with the above-mentioned organic polymers; polysulfide-based polymers; nylon by ring-opening polymerization of ε-caprolactam. 6. Nylon 6.6 by polycondensation of hexamethylenediamine and adipic acid, nylon 6/10 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of ε-aminoundecanoic acid, ε-aminolaurolactam Nylon 12 by ring-opening polymerization, polyamide-based polymers such as copolymerized nylon having two or more components among the above nylons; for example, polycarbonate-based polymers produced by condensation polymerization of bisphenol A and carbonyl chloride; diallyl phthalate Examples include system polymers.

Among the above-mentioned polymers having a main chain skeleton, polyoxyalkylene polymers, hydrocarbon polymers, polyester polymers, vinyl copolymers, polycarbonate polymers are easy to obtain and manufacture. Polymers and the like are preferred. Furthermore, saturated hydrocarbon polymers, polyoxyalkylene polymers, and vinyl copolymers are particularly preferable because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance.

The saturated hydrocarbon polymer having a reactive silicon group used in the present invention includes a reactive silicon group derived from a saturated hydrocarbon polymer such as polyisobutylene, hydrogenated polybutadiene and hydrogenated polyisoprene. Examples include saturated hydrocarbon polymers.

The reactive silicon group contained in the organic polymer having a reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and is accelerated by the carboxylic acid metal salt as the component (B). It is a group that can be crosslinked by the formation of a siloxane bond which is a reaction.

The reactive silicon group is represented by the general formula (1):

[0031]

[Chemical 3] (In the formula, R ¹ and R ² each independently have 1 to 1 carbon atoms.
20 alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms (R ') ₃ SiO-
(R's are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), which is a triorganosiloxy group. Further, X is independently a hydroxyl group or a hydrolyzable group. Furthermore, a is 0, 1,
It is either 2, 3, b is 0, 1, 2, and a and b are never 0 at the same time. Also, m
Is 0 or an integer of 1 to 19).

The hydrolyzable group is not particularly limited,
Any conventionally known hydrolyzable group may be used. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
Examples thereof include commonly used groups such as acid amide group, aminooxy group, mercapto group and alkenyloxy group.

Of these, an alkoxy group, an amide group and an aminooxy group are preferable, but an alkoxy group is particularly preferable because it has mild hydrolyzability and is easy to handle.

The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + Σ
The range of b) is preferably 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

The number of silicon atoms forming the reactive silicon group is 1
The number is not less than 20 but is preferably not more than 20 in the case of silicon atoms connected by a siloxane bond or the like.

In particular, the general formula (13):

[0037]

[Chemical 4] (In formula, R < ² >, X is the same as the above. C is an integer of 1-3.)
The reactive silicon group represented by is preferable because it is easily available.

Specific examples of the above general formula (13) when c is 3 include trialkoxysilyl groups such as methoxy, ethoxy, propoxy and isopropoxy. In the above general formula (13), c
When R is not 3, specific examples of R ² include, for example, alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and R ′. Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— such as a methyl group and a phenyl group. Of these, a methyl group is particularly preferred because of its high activity of hydrolysis reaction.

Specific examples of the reactive silicon group include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group and diisopropoxymethylsilyl group. Can be mentioned. In particular, the trimethoxysilyl group is preferable because it has high activity and can reduce the amount of the carboxylic acid metal salt as the component (B).

The introduction of the reactive silicon group may be carried out by a known method. That is, for example, the following method can be used.

(A) An organic polymer having a functional group such as a hydroxyl group in a molecule is reacted with an organic compound having an active group and an unsaturated group reactive with the functional group to contain an unsaturated group. To obtain an organic polymer. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Then, the obtained reaction product is subjected to hydrosilylation by reacting hydrosilane having a reactive silicon group.

(B) A compound having a mercapto group and a reactive silicon group is reacted with the unsaturated group-containing organic polymer obtained in the same manner as in the method (a).

(C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a functional group reactive with this functional group and a reactive silicon group. .

Among the above methods, the method (a) or (c) a polymer having a hydroxyl group at the terminal and a compound having an isocyanate group and a reactive silicon group are used in view of the reduction of the production cost. Is preferred.

Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; trimethoxysilane, triethoxysilane and methyl. Alkoxysilanes such as diethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; Acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; Bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) ) Ketoximate silanes such as methylsilane can be mentioned, but the invention is not limited thereto. Among these, from the viewpoint of availability and high hydrolysis reactivity,
Particularly, halogenated silanes and alkoxysilanes are preferable.

As the synthetic method of (b), for example, a compound having a mercapto group and a reactive silicon group is subjected to a radical addition reaction in the presence of a radical initiator and / or a radical generation source to unsaturated the organic polymer. Examples of the method include introduction into the binding site, but the method is not particularly limited. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxy. Examples thereof include, but are not limited to, silane.

As the method of reacting the polymer having a hydroxyl group at the terminal with the compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method disclosed in JP-A-3-47825 can be used. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatopropylmethyldiethoxy. Examples thereof include, but are not limited to, silane.

A disproportionation reaction may proceed in a silane compound such as trimethoxysilane in which three hydrolyzable groups are bonded to one silicon atom. When the disproportionation reaction progresses,
This produces fairly dangerous compounds such as dimethoxysilane. However, with γ-mercaptopropyltrimethoxysilane and γ-isocyanatopropyltrimethoxysilane, such disproportionation reaction does not proceed. Therefore, when a group in which three hydrolyzable groups such as a trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthetic method (b) or (c) should be used. preferable.

The number average molecular weight of the organic polymer as the component (A) is preferably about 500 to 50,000 in terms of polystyrene in GPC (gel permeation chromatography), and particularly about 1,000 to 30,000. Those having liquid or fluidity are preferable from the viewpoint of easy handling. When the number average molecular weight is less than 500, sufficient rubber elasticity cannot be obtained, and when it exceeds 50,000, it is not preferable because it has poor fluidity at room temperature and is difficult to handle.

The number of reactive silicon groups in one molecule of the organic polymer as the component (A) is 1 or more, preferably 1.1 to 5. The number of reactive silicon groups contained in the molecule is 1
If it is less than 5, the curability may be insufficient and good rubber elasticity may not be obtained, and if it is more than 5, the rubber may become hard and brittle, resulting in poor rubber elasticity.

The reactive silicon group may be at the main chain terminal or side chain of the organic polymer, or at both of them. Especially when the reactive silicon group is at the end of the main chain,
Since the organic polymer component contained in the finally formed cured product has a large amount of effective network chains, it is preferable in that a rubber-like cured product having high strength and high elongation can be easily obtained.

The polyoxyalkylene polymer essentially has the general formula (14):

[0053]

[Chemical 5] (In the formula, R ³ is a divalent organic group and is a linear or branched alkylene group having 1 to 14 carbon atoms.) A polymer having a repeating unit represented by the general formula (14) R ³ is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (14) include:

[0054]

[Chemical 6] Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one kind of repeating unit or may be composed of two or more kinds of repeating units. Especially when it is used as a sealant or the like, a polymer mainly composed of a polyoxypropylene polymer is preferable because it is amorphous and has a relatively low viscosity.

The polyoxyalkylene polymer can be synthesized, for example, by a polymerization method using an alkali catalyst such as KOH, or a complex obtained by reacting an organoaluminum compound disclosed in JP-A-61-215623 with porphyrin. Polymerization method using a transition metal compound-porphyrin complex catalyst such as JP-B-46-27250 and JP-B-59-
15336, US Pat. No. 3,278,457, US Patent 3
No. 278458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S. Pat. No. 3,427,334, and U.S. Pat. No. 3,427,335. Examples of the method include, but are not particularly limited to, a polymerization method using a catalyst and a polymerization method using a catalyst containing a phosphazene compound exemplified in JP-A No. 11-060722.

The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

The urethane bonding component is not particularly limited, and examples thereof include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. Examples thereof include those obtained by reacting a polyisocyanate compound with a polyol having a repeating unit represented by the general formula (14).

A method for producing a polyoxyalkylene polymer having a reactive silicon group is described in JP-B-45-36319.
No. 4, Japanese Patent Publication No. 46-12154, JP-A No. 50-1565.
99, JP-A-54-6096, JP-A-55-137.
67, JP-A-55-13468, JP-A-57-16
4123, Japanese Examined Patent Publication No. 3-2450, US Pat.
557, U.S. Pat. No. 4,345,053, U.S. Pat.
6307, U.S. Pat. No. 4,960,844, and the like, and those disclosed in JP-A-61-197631,
JP-A-61-215622, JP-A-61-21562
3, JP-A-61-218632, JP-A-3-725.
27, JP-A-3-47825, and JP-A-8-2317.
No. 07, the number average molecular weight is 6,0.
A polyoxyalkylene polymer having a high molecular weight of 00 or more and Mw / Mn (ratio of weight average molecular weight to number average molecular weight) of 1.6 or less and a narrow molecular weight distribution can be preferably used, but is not particularly limited thereto. Not a thing.

The above polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more kinds.

The polymer forming the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used in the present invention is (1) an olefin having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene. Obtained by a method of polymerizing a main compound as a main component, (2) homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing with the above olefin compound and then hydrogenating. However, an isobutylene-based polymer or a hydrogenated polybutadiene-based polymer is preferable because it is easy to introduce a functional group into the terminal, the molecular weight is easily controlled, and the number of terminal functional groups can be increased.

In the isobutylene-based polymer, all the monomer units may be formed of isobutylene units,
The amount of the monomer unit copolymerizable with isobutylene in the isobutylene polymer is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight.
You may contain in the following ranges. In the isobutylene-based polymer, when the content of the monomer unit having a copolymerizability with isobutylene exceeds 50% by weight, characteristic properties such as high weather resistance, high heat resistance and low moisture permeability due to the isobutylene skeleton Is not expressed sufficiently, which is not preferable.

As such a monomer component, for example,
Examples thereof include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes and allylsilanes. Examples of such a copolymer component include 1-butene, 2-butene, 2-methyl-1-butene,
3-methyl-1-butene, pentene, 4-methyl-1-
Pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β
-Pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane,
Vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,
1,3,3-Tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyl Examples thereof include dimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

If vinyl silanes or allyl silanes are used as the monomer units having a copolymerizability with isobutylene, the silicon content increases and the number of groups capable of acting as a silane coupling agent increases. The adhesiveness of the composition is improved.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers as well, as in the case of the above-mentioned isobutylene-based polymer, other monomer units other than the main component monomer unit are added. It may be contained.

In the saturated hydrocarbon polymer having a reactive silicon group used in the present invention, a double bond after polymerization such as a polyene compound such as butadiene and isoprene is contained within a range in which the object of the present invention can be achieved. The residual monomer unit may be contained in a small amount, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

These saturated hydrocarbon polymers having a reactive silicon group can be used alone or in combination of two or more kinds.

Next, a method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described.

Among the isobutylene-based polymers having a reactive silicon group, the isobutylene-based polymer having a reactive silicon group at the terminal of the molecular chain is a polymerization method called an inifer method (initiator called an inifer and a chain transfer agent are also used. It can be produced by using a terminal functional type, preferably all terminal functional type isobutylene polymer obtained by a cationic polymerization method using a specific compound described above. As a method for producing a saturated hydrocarbon polymer having a reactive silicon group, for example, a dehydrohalogenation reaction at the terminal of a polymer having a tertiary carbon-chlorine bond obtained by a polymerization reaction, or a tertiary carbon-chlorine bond is used. After obtaining a polyisobutylene having an unsaturated group at the terminal by reaction of the terminal of the polymer having with allyltrimethylsilane, the general formula (15):

[0069]

[Chemical 7] (In the formula, R ¹ , R ² , X, m, a and b are the same as above.) (This compound is a compound in which a hydrogen atom is bonded to the group represented by the general formula (1). Of the general formula (16):

[0070]

[Chemical 8] (In the formula, R ² , X and c are the same as above.), And can be obtained by a reaction (hydrosilylation reaction) of adding a hydrosilane compound using a platinum catalyst.

Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; trimethoxysilane, triethoxysilane,
Alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane;
Acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; and ketoxymate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane. It is not limited. Among these, halogenated silanes and alkoxysilanes are preferable in view of easy availability.

Such a manufacturing method is described in, for example, Japanese Patent Publication No.
69659, Japanese Examined Patent Publication No. 7-108928, JP-A-63
-254149, Japanese Patent Laid-Open No. 64-22904, and Japanese Patent No. 2539445.

The isobutylene-based polymer having a reactive silicon group on the side chain of the molecular chain is prepared by adding vinylsilanes or allylsilanes having a reactive silicon group to a monomer containing isobutylene and copolymerizing them. Manufactured.

Further, in the polymerization reaction for producing an isobutylene polymer having a reactive silicon group at the terminal of the molecular chain, vinylsilanes and allylsilanes having a reactive silicon group are co-produced in addition to the main component isobutylene monomer. After the polymerization, the reactive silicon group is introduced into the terminal to produce an isobutylene polymer having a reactive silicon group at the terminal and the side chain of the molecular chain.

Examples of vinylsilanes and allylsilanes having a reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane and allyl. Examples thereof include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropylmethyldimethoxysilane.

In the present invention, examples of the saturated hydrocarbon polymer having a reactive silicon group include a hydrogenated polybutadiene polymer having a reactive silicon group.
The hydrogenated polybutadiene polymer having a reactive silicon group is
It can be obtained by a hydrosilylation reaction of a hydrogenated polybutadiene polymer having an olefin group. Hydrogenated polybutadiene-based polymer having a terminal olefin group, for example,
First, after the hydroxyl group of hydroxy-terminated hydrogenated polybutadiene polymer oxy metal group such -ONa or -OK, the general formula _{(17): CH 2 = CH} -R 4 -Y (17) wherein, Y Is a halogen atom such as chlorine atom, bromine atom or iodine atom, R ⁴ is —R ⁵ —, —R ⁵ —OCO— or —
R ⁵ —CO— (R ⁵ is a divalent hydrocarbon group having 1 to 20 carbon atoms and is preferably an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group), and is —CH. _{2 -, - R "-C 6} H 4 -CH 2 - (R" is a hydrocarbon group having 1 to 10 carbon atoms) by reacting the organic halogen compound represented by particularly preferred] is a divalent group selected from Can be obtained by

The method of converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer into an oxymetal group is as follows:
Alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; Na
Examples thereof include a method of reacting with an alkali hydroxide such as OH and KOH.

In the above method, a terminal olefin hydrogenated polybutadiene polymer having a molecular weight almost the same as that of the terminal hydroxy hydrogenated polybutadiene polymer used as the starting material can be obtained. However, when a higher molecular weight polymer is desired, Is methylene chloride, bis (chloromethyl) benzene, before reacting with the organohalogen compound of the general formula (17),
The molecular weight can be increased by reacting with a polyvalent organic halogen compound containing two or more halogens in one molecule such as bis (chloromethyl) ether, and then the organic halogen compound represented by the general formula (17). When reacted with, a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained.

Specific examples of the organic halogen compound represented by the general formula (17) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl ( Chloromethyl) ether,
Examples include, but are not limited to, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, and allyloxy (chloromethyl) benzene. Of these, allyl chloride is inexpensive,
Moreover, it is preferable because it reacts easily.

The introduction of the reactive silicon group into the hydrogenated polybutadiene polymer having a terminal olefin is carried out by using a platinum catalyst as the hydrosilane compound in the same manner as in the case of the isobutylene polymer having a reactive silicon group at the terminal of the molecular chain. It can be produced by carrying out an addition reaction.

When the saturated hydrocarbon polymer having a reactive silicon group does not substantially contain an unsaturated bond which is not an aromatic ring in the molecule as described above, an organic polymer having an unsaturated bond or The weather resistance is remarkably improved as compared with a sealing agent made of a conventional rubber polymer such as an oxyalkylene polymer. Further, since the polymer is a hydrocarbon polymer, a cured product having good water resistance and low moisture permeability can be obtained.

These organic polymers having a reactive silicon group may be used alone or in combination of two or more kinds. Specifically, a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, a vinyl polymer having a reactive silicon group,
An organic polymer obtained by blending two or more selected from the group consisting of can also be used.

A method for producing an organic polymer prepared by blending a polyoxyalkylene polymer having a reactive silicon group and a vinyl polymer having a reactive silicon group is described in JP-A-5-52.
No. 9-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763 are disclosed, but the invention is not limited thereto.

A preferred specific example is a compound having a reactive silicon group and having a molecular chain substantially the following general formula (18):

[0085]

[Chemical 9] (In the formula, R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a carbon atom 1
A (meth) acrylic acid ester monomer unit having an alkyl group having 1 to 8 carbon atoms represented by the following general formula (19):

[0086]

[Chemical 10] (Wherein R ⁶ is the same as above, R ⁸ represents an alkyl group having 10 or more carbon atoms), and is a copolymer of (meth) acrylic acid ester monomer units having an alkyl group having 10 or more carbon atoms. In this method, a polyoxyalkylene polymer having a reactive silicon group is blended with the polymer. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

R in the general formula (18)⁷As
For example, methyl group, ethyl group, propyl group, n-butyl group,
1 to 6 carbon atoms such as t-butyl group and 2-ethylhexyl group
8, preferably 1 to 4, more preferably 1 to 2 al
A kill group is given. In addition, R ⁷The alkyl group of
Also, two or more kinds may be mixed.

R ^{8 in the} above general formula (19) is, for example, a lauryl group, a tridecyl group, a cetyl group, a stearyl group or a behenyl group having 10 or more carbon atoms, usually 10 to 3 carbon atoms.
There may be mentioned 0, preferably 10 to 20 long-chain alkyl groups. In addition, the alkyl group of R ⁸ may be a single kind or a mixture of two or more kinds as in the case of R ⁷ .

The molecular chain of the vinyl-based copolymer is substantially composed of the monomer units of the formula (18) and the formula (19). This means that the sum of the monomer units of formula (18) and formula (19) present is greater than 50% by weight. Equation (18) and Equation (1
The total of the monomer units of 9) is preferably 70% by weight or more.

Further, the monomer unit of the formula (18) and the formula (19)
The abundance ratio of the monomer units is 95: 5 to 40:60 in terms of weight ratio from the viewpoint of compatibility with the polyoxyalkylene polymer.
Is preferred, and 90:10 to 60:40 is more preferred.

Formula (1) which may be contained in the copolymer
Examples of the monomer units other than 8) and the formula (19) include carboxylic acid groups such as acrylic acid and methacrylic acid, amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and glycidyl. Monomers containing epoxy groups such as acrylate and glycidyl methacrylate, amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, propion Examples thereof include monomer units derived from vinylate, ethylene and the like.

An organic polymer prepared by blending a saturated hydrocarbon-based polymer having a reactive silicon group and a vinyl-based polymer having a reactive silicon group is disclosed in JP-A-1-168864.
No. 2000-186176, etc., but is not particularly limited thereto.

Further, as a method for producing an organic polymer prepared by blending a vinyl polymer having a reactive silicon group, another method is to produce a (meth) acryl in the presence of an organic polymer having a reactive silicon group. A method of polymerizing an acid ester monomer can be used. This manufacturing method is disclosed in JP-A-59-78.
223, JP-A-59-168014, JP-A-60-
It is specifically disclosed in JP-A No. 228516 and JP-A No. 60-228517, but the invention is not limited thereto.

Calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate used as component (B) in the curable composition of the present invention, One or more carboxylic acid metal salts selected from cobalt carboxylate and zirconium carboxylate are siloxane bonds from a silicon atom-bonded hydroxyl group or hydrolyzable group contained in the organic polymer as the component (A) of the present invention. And functions as a so-called silanol condensation catalyst.

Among the metal carboxylates, calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate and zirconium carboxylate have high catalytic activity. More preferred from the viewpoint, calcium carboxylate, vanadium carboxylate, iron carboxylate,
Titanium carboxylate and zirconium carboxylate are more preferable, and iron carboxylate and titanium carboxylate are most preferable.

Calcium carboxylate, vanadium carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate and zirconium carboxylate are used for coloring the curable composition to be obtained. Is more preferable, and the obtained cured product has high heat resistance and weather resistance, and calcium carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, and zirconium carboxylate are more preferable.

The component (B) has the general formula (2).
To (12) are main components of the carboxylic acid metal salt. Ca (OCOR) ₂ (2) V (OCOR) ₃ (3) Fe (OCOR) ₂ (4) Fe (OCOR) ₃ (5) Ti (OCOR) ₄ (6) K (OCOR) (7) Ba (OCOR) ) ₂ (8) Mn (OCOR) ₂ (9) Ni (OCOR) ₂ (10) Co (OCOR) ₂ (11) Zr (O) (OCOR) ₂ (12) (wherein R is substituted or unsubstituted) It is a hydrocarbon group and may contain a carbon-carbon double bond.) Here, as the carboxylic acid, a hydrocarbon-based carboxylic acid group-containing compound having 2 to 40 carbon atoms including carbonyl carbon is preferable. From the viewpoint of availability, a hydrocarbon-based carboxylic acid group-containing compound having 2 to 20 carbon atoms can be particularly preferably used.

Specific examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecyl acid, myristic acid. Linear saturated fatty acids such as acids, pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, laxeric acid; undecylenic acid, linderic acid , Tudus acid, fizeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid,
7-hexadecenoic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadoleic acid, gondoinic acid, cetrainic acid,
Monoene unsaturated fatty acids such as erucic acid, brassic acid, ceracoleic acid, ximene acid, and lumecic acid; linoleic acid, 10,12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid , Punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,
8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,
19-docosatetraenoic acid, 4,8,12,15,18
-Polyene unsaturated fatty acids such as eicosapentaenoic acid, sardine acid, nisinic acid and docosahexaenoic acid; isoacids,
Branched fatty acids such as anteisoic acid, tuberculostearic acid, pivalic acid and neodecanoic acid; fatty acids having triple bonds such as talylinic acid, stearolic acid, krepenic acid, ximenic acid and 7-hexadecic acid; naphthenic acid, Alicyclic carboxylic acids such as malvalic acid, sterculic acid, hydronocarbic acid, shoalmoogric acid, and golulinic acid; sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambretic acid Contains tolric acid, aleuritic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camrolenic acid, licanoic acid, ferronic acid, cerebronic acid, etc. Oxygen fat Acids; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dicarboxylic acids such as sebacic acid.

When the carboxylic acid has a high melting point (high crystallinity), the carboxylic acid metal salt having the acid group also has a high melting point and is difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is 6
The temperature is preferably 5 ° C. or lower, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

When the carbon number of the carboxylic acid is large (the molecular weight is large), the carboxylic acid metal salt having the acid group becomes solid or liquid with high viscosity and is difficult to handle (poor workability). Will be things. Conversely, when the carbon number of the carboxylic acid is small (the molecular weight is small),
The carboxylic acid metal salt having an acid group contains a large amount of components that are easily volatilized by heating, and the catalytic ability of the carboxylic acid metal salt may be reduced. In particular, under the condition that the composition is thinly stretched (thin layer), volatilization by heating is large, and the catalytic ability of the carboxylic acid metal salt may be greatly reduced. Therefore, the carboxylic acid has preferably 2 to 17 carbon atoms, more preferably 3 to 13 carbon atoms, and particularly preferably 5 to 10 carbon atoms, including the carbon atoms of the carbonyl group.

Especially, since the carboxylic acid is easily available and inexpensive and has good compatibility with the component (A),
-Ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, naphthenic acid and the like are preferable. The naphthenic acid is represented by the composition formula (20). C _n H _2n-2 O ₂ (20) Further, the carboxylic acid is a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a tertiary carbon (2-ethylhexanoic acid, etc.) or a quaternary carbon. Acids (neodecanoic acid, pivalic acid, etc.) are more preferable because the curing rate is fast, and carboxylic acids in which the carbon atom adjacent to the carbonyl group is a quaternary carbon are particularly preferable.

From the viewpoint of availability and compatibility, specific examples of preferable metal salts of carboxylic acid include iron 2-ethylhexanoate (divalent), iron 2-ethylhexanoate (trivalent), 2-ethylhexanoic acid. Titanium (tetravalent), vanadium 2-ethylhexanoate (trivalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (1
Value), barium 2-ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent), nickel 2-ethylhexanoate (divalent), cobalt 2-ethylhexanoate (divalent), 2-ethyl Zirconium hexanoate (4
Value), iron neodecanoate (divalent), iron neodecanoate (3
Valent), titanium neodecanoate (tetravalent), vanadium neodecanoate (trivalent), calcium neodecanoate (2)
Value), potassium neodecanoate (monovalent), barium neodecanoate (divalent), zirconium neodecanoate (tetravalent),
Iron oleate (divalent), iron oleate (trivalent), titanium oleate (tetravalent), vanadium oleate (3)
Value), calcium oleate (divalent), potassium oleate (monovalent), barium oleate (divalent), manganese oleate (divalent), nickel oleate (divalent), cobalt oleate (divalent) , Zirconium oleate (tetravalent), iron naphthenate (divalent), iron naphthenate (3
Valent), titanium naphthenate (tetravalent), vanadium naphthenate (trivalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate (2)
Valent), manganese naphthenate (divalent), nickel naphthenate (divalent), cobalt naphthenate (divalent), zirconium naphthenate (tetravalent), and the like.

From the viewpoint of catalytic activity, iron 2-ethylhexanoate (divalent), iron 2-ethylhexanoate (trivalent), 2-
Titanium ethylhexanoate (tetravalent), iron neodecanoate (divalent), iron neodecanoate (trivalent), titanium neodecanoate (tetravalent), iron oleate (divalent), iron oleate (trivalent), olein Titanium acid (tetravalent), iron naphthenate (divalent), iron naphthenate (trivalent), titanium naphthenate (tetravalent) are more preferable, iron 2-ethylhexanoate (trivalent), iron neodecanoate (3) Value), iron oleate (3
Values) and iron naphthenate (trivalent) are particularly preferable.

From the viewpoint of coloring, titanium 2-ethylhexanoate (tetravalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (1
Valence), barium 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), titanium neodecanoate (tetravalent), calcium neodecanoate (divalent),
Potassium neodecanoate (monovalent), barium neodecanoate (divalent), zirconium neodecanoate (tetravalent), titanium oleate (tetravalent), calcium oleate (2)
Value), potassium oleate (monovalent), barium oleate (divalent), zirconium oleate (tetravalent), titanium naphthenate (tetravalent), calcium naphthenate (2)
Valence), potassium naphthenate (monovalent), barium naphthenate (divalent), and zirconium naphthenate (tetravalent) are more preferable.

Such a carboxylic acid metal salt is prepared by reacting a carboxylic acid group-containing compound or its ester with sodium hydroxide to prepare an aqueous solution of sodium soap. Precipitation method of precipitating metal soap, melting method of reacting carboxylic acid group-containing compound or its ester with metal hydroxide, oxide, weak acid salt at high temperature, direct reaction of carboxylic acid group-containing compound and metal powder In addition to the method, a method of reacting an alcoholate or chloride with a carboxylic acid group-containing compound in an anhydrous organic solvent may be used.

Such a carboxylic acid metal salt is diluted with a diluting solvent such as mineral spirit, toluene, hexylene glycol, diethylene glycol, white kerosene or dioctyl phthalate to prepare a solution having a metal content of about 1 to 40% by weight. It is preferably used in the form.

The amount of the component (B) used is preferably about 0.005 to 5 parts by weight in terms of the metal element contained in the component (B), and more preferably 0 to 100 parts by weight of the component (A). About 0.01 to 3 parts by weight is preferable. If the blending amount of the component (B) is less than this range, the curing rate may be slow and the curing reaction may not be able to proceed sufficiently, which is not preferable. On the other hand, if the content of the component (B) exceeds this range, local heat generation and foaming will occur during curing, and it will be difficult to obtain a good cured product, and the pot life will be too short, and workability will be improved. Not preferable.

The above-mentioned calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate and zirconium carboxylate may be used alone. Besides being used, they can be used in combination of two or more kinds, and can be used in combination with tin carboxylate, lead carboxylate, bismuth carboxylate, cerium carboxylate and the like.

On the other hand, when the activity of the carboxylic acid metal salt of the component (B) is low and an adequate curability cannot be obtained, various amine compounds as the component (C) can be added as a cocatalyst. As various amine compounds, for example,
As described in JP-A-5-287187, specifically, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, lauryl. Aliphatic primary amines such as amine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl)
Aliphatic secondary amines such as amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine and butylstearylamine; fats such as triethylamine, triamylamine, trihexylamine and trioctylamine Group tertiary amines; aliphatically unsaturated amines such as triallylamine and oleylamine; laurylaniline, stearylaniline, triphenylamine, N, N
-Aromatic amines such as dimethylaniline and dimethylbenzylaniline; and as other amines, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, benzylamine, Diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, dodecamethylenediamine, dimethylethylenediamine, triethylenediamine, guanidine,
Diphenylguanidine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-
Tetramethylethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and the like can be mentioned, but not limited thereto.

In the present invention, an amino group-containing silane coupling agent can also be used as the component (C).
The amino group-containing silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and an amino group.
Examples of this hydrolyzable silicon group include those in which X is a hydrolyzable group among the groups represented by formula (1). Specific examples of the hydrolyzable group include the groups already exemplified, but a methoxy group and an ethoxy group are preferable from the viewpoint of the hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly preferably 3 or more.

Specific examples of the amino group-containing silane coupling agent include γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-Aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-
(2-Aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples thereof include benzyl-γ-aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane. Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and the like, which are modified derivatives thereof, can also be used. The amino group-containing silane coupling agent may be used alone or in combination of two or more.

As the component (C), the cocatalyst ability greatly varies depending on the structure of the component (C) itself, the compatibility with the component (A), and the like. Therefore, a compound suitable for the type of the component (A) to be used. Is preferred. For example, when an isobutylene-based polymer is used as the component (A), a relatively long-chain aliphatic secondary amine such as dioctylamine or distearylamine or an aliphatic secondary amine such as dicyclohexylamine is used as a promoter. Is preferred from the standpoint of high.

The blending amount of the amine compound as the component (C) is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the organic polymer as the component (A).
More preferably parts by weight. Amount of amine compound is 0.0
If it is less than 1 part by weight, the curing speed may be slow,
Further, it may be difficult for the curing reaction to proceed sufficiently. On the other hand, if the compounding amount of the amine compound exceeds 20 parts by weight, the pot life may be too short, which is not preferable from the viewpoint of workability.

A silane coupling agent other than the amino group-containing silane coupling agent can be used in the composition of the present invention.

Examples of functional groups other than amino groups include mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens.

Specific examples of the silane coupling agent other than the amino group-containing silane coupling agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyl. Mercapto group-containing silanes such as methyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, β-
Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β-
Carboxysilanes such as (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-
Vinyl-type unsaturated group-containing silanes such as methacryloyloxypropylmethyldimethoxysilane and γ-acroyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; tris (trimethoxysilyl) isocyanurate Isocyanurate silanes such as; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and other isocyanate group-containing silanes You can In addition, blocked isocyanate silanes, silylated polyesters, and the like, which are modified derivatives thereof, can also be used as the silane coupling agent.

When a silane coupling agent other than the amino group-containing silane coupling agent is used, the amount used is (A)
The amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the component.

Various fillers can be used in the curable composition of the present invention as required. Specific examples of the filler include, for example, wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder,
Rice husk powder, graphite, diatomaceous earth, clay, fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, aluminum hydroxide, magnesium carbonate. , Aluminum fine powder, flint powder, zinc powder and the like. Among these fillers, precipitated silica, fume silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc, etc. are included in terms of reinforcing effect, increasing effect, and easy availability. preferable. These fillers may be used alone or in combination of two or more.
The amount of the filler used is preferably 10 to 1000 parts by weight, and preferably 50 to 30 parts by weight, per 100 parts by weight of the component (A).
0 weight part is more preferable.

In the curable composition of the present invention, it is more effective to use the plasticizer in combination with the filler since the elongation of the cured product can be increased and a large amount of the filler can be mixed. Specific examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate,
Phthalates such as diisodecyl phthalate and diisoundecyl phthalate; Aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate and dioctyl sebacate; Glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester Aliphatic esters such as butyl oleate and methyl acetylricinoleate; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate; epoxidized soybean oil, epoxidized linseed oil, epoxystearic acid Epoxy plasticizers such as benzyl; polyester-based plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and its derivatives; poly-α -Polystyrenes such as methylstyrene and polystyrene; polybutadiene, butadiene-
Examples thereof include acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrocarbon oligomers such as process oil, and chlorinated paraffins.

These plasticizers may be used alone or in combination of two or more kinds. When the amount of the plasticizer is 1 to 200 parts by weight based on 100 parts by weight of the reactive silicon group-containing organic polymer, preferable results are obtained.

In the curable composition of the present invention, an epoxy resin can be used together. In this case, the epoxy resin and the reactive silicon group-containing organic polymer can be modified.

As the epoxy resin, conventionally known ones can be widely used. Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, Hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, etc. Phthalic acid diglycidyl ester epoxy resin, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N N- diglycidyl aniline,
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, etc. Can be mentioned.

Among these epoxy resins, those containing at least two epoxy groups in the molecule are preferable because they have high reactivity during curing and the cured product easily forms a three-dimensional network structure. More preferable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin and phthalic acid diglycidyl ester type epoxy resin from the viewpoint of availability and adhesiveness.

As the curing agent for the epoxy resin, conventionally known curing agents for epoxy resin can be widely used, and examples thereof include triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, Amines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine salts, polyamide resins, ketimines, aldimines, enamines Latent hardeners such as imidazoles,
Dicyandiamides, boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic anhydride, carboxylic anhydrides such as chlorenic anhydride , Alcohols, phenols, carboxylic acids and the like.

The epoxy resin is used in an amount of 1 to 100 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the reactive silicon group-containing organic polymer.
It is preferable to use in the range of 0 to 50 parts by weight, and the curing agent for the epoxy resin is 1 per 100 parts by weight of the epoxy resin.
It is preferable to blend in an amount of up to 200 parts by weight, more preferably 10 to 100 parts by weight.

The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-mentioned components are blended and kneaded at room temperature or under heating with a mixer, roll, kneader or the like, and a suitable solvent is added. Conventional methods such as using a small amount to dissolve the components and mixing can be adopted. Further, by appropriately combining these components, a one-pack type, a two-pack type or a multi-pack type compound can be prepared and used.

The curable composition of the present invention, when exposed to the atmosphere, forms a three-dimensional network structure by the action of water and cures into a solid having rubber-like elasticity.

Various additives can be added to the curable composition of the present invention as required. Examples of the additives include, for example, other curing catalysts (such as tetravalent tin and 2
Tin, etc.), a physical property adjusting agent that adjusts the tensile properties of the resulting cured product, an adhesiveness-imparting agent such as a silane coupling agent,
Antioxidants, radical inhibitors, UV absorbers, metal deactivators, antiozonants, light stabilizers, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, photocurable resins, thixotropic properties Examples include agents.

Specific examples of such additives are described, for example, in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149 and JP-A-64-22904. Has been done.

The curable composition of the present invention has excellent weather resistance, heat resistance, water resistance, and electrical insulation due to the main chain skeleton, and also has the effect of improving physical properties such as high strength and high elongation. Therefore, elastic sealing materials for construction and sealing materials for double-layer glass, electrical / electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, paints, It can be suitably used as an injection material, a coating material, and a rust / waterproof sealing material. It is especially useful when used as an adhesive, an elastic sealing material for construction, or a sealing material for siding.

[0131]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. (Examples 1 to 4 and Comparative Example 1) Isobutylene-based polymer having a reactive silicon group as the component (A) (Kanefuchi Chemical Industry Co., Ltd., trade name EP505S: isobutylene-based polymer / paraffin-based process oil = 100/50) 150
5 parts by weight of epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), hydrogenated α
-Olefin oligomer (manufactured by Idemitsu Petrochemical Co., Ltd., trade name PAO5004) 60 parts by weight, colloidal calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name Cilets 200)
50 parts by weight, colloidal calcium carbonate (Maruo Calcium Co., Ltd., trade name MC-5) 50 parts by weight, heavy calcium carbonate (Shiraishi Calcium Co., Ltd., trade name Softon 32)
00) 40 parts by weight, photocurable resin (manufactured by Toagosei Co., Ltd.,
Product name Aronix M-309) 3 parts by weight, benzotriazole-based ultraviolet absorber (manufactured by Nippon Ciba Geigy Co., Ltd.,
Trade name TINUVIN 327) 1 part by weight, hindered amine light stabilizer (manufactured by Sankyo Co., Ltd., trade name SANOL LS-77)
0) 1 part by weight, hindered phenolic antioxidant (manufactured by Nippon Ciba Geigy Ltd., trade name Irganox 101)
0) 1 part by weight and 5 parts by weight of water were weighed and kneaded well with a triple paint roll to prepare a main agent.

Next, as the component (B), octyl acid (2-
Ethylhexanoic acid) calcium salt (Japan Chemical Industry Co., Ltd.)
(Trade name, Nikka Octix Ca 5% toluene solution), and distearylamine (Pharmine D86, manufactured by Kao Corporation) as the component (C) are each weighed in the parts shown in Table 1, and well stirred using a spatula. The mixture was used as the curing agent in Example 1.

Here, vanadium naphthenate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name Nikka Naphtex V 2% toluene solution) is used as the component (B) of the present invention, and distearylamine (Kao (stock) is used as the component (C). ), Farmin D8
Example 2 was prepared by using 6) for each of the weight parts shown in Table 1.
Octylic acid (2-ethylhexanoic acid) iron (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name Nikka Octix Fe 6% toluene solution) as the component (B), and laurylamine (Wako Pure Chemical Industries, Ltd.) as the component (C). (Manufactured by K.K.) was used in each of the parts by weight shown in Table 1 as Example 3, and (B)
Octaic acid (2-ethylhexanoic acid) titanium (3% toluene solution) was used as a component, and laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a component (C) in parts by weight shown in Table 1, respectively. It was set to 4. On the other hand, (B) tin octylate (2-ethylhexanoate) (Nitto Kasei Co., Ltd.)
Comparative Example 1 was manufactured by Neostan U-28) and used laurylamine as the component (C) in parts by weight shown in Table 1.

Table 1 shows the main agent and the curing agent, respectively.
Are mixed in the ratio shown in, and this is mixed with JISA 5758-199.
According to the method for producing the tensile adhesion test body specified in 2, an aluminum base material was assembled in an H-shape and filled. Curing condition is 2
It was set to 3 ° C. × 7 days + 50 ° C. × 7 days. The aluminum used as the base material is 50 x 5 in accordance with JIS H4000.
Using 0x5 mm size anodized aluminum, after cleaning with methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) before filling the compound, a primer (manufactured by Toray Dow Corning, trade name D-2) ) Was applied and dried at room temperature for 30 minutes before use.

The H-shaped sample obtained by the above method is J
According to the tensile adhesion test method specified in IS A5758-1992, in a thermostatic chamber at 23 ° C. and a humidity of 50 ± 5%, a pulling speed of 5
The test was performed under the condition of 0 mm / min.

The restoration rate was measured by the following method. First, the H-shaped sample that had been cured was immersed in warm water at 50 ° C. for 1 day, taken out, and then left at room temperature for 1 day. The sample is then sampled to a thickness of 12 mm to 8.4 mm
The mixture was compressed and fixed to 70% so that it became, and heated for 1 day in a hot air dryer at 100 ° C., then released from compression and left at room temperature for 1 day. The thickness of the sample at this time was measured, and the restoration rate for the compressed portion was calculated.

As a measure for estimating the curability, the same composition was simultaneously packed in an ointment can at 23 ° C. and a relative humidity of 50%.
The time until the surface was stretched (skinning time) was measured under the conditions of. The shorter the skinning time is, the higher the curability is.

The results are shown in Table 1. The CF in the table, which represents the fracture state, means that the filled cured product exhibits cohesive fracture, which is the fracture state required for the sealing material.

[0139]

[Table 1] As shown in Table 1, an isobutylene polymer is used as the component (A), calcium octylate is used as the component (B),
When vanadium naphthenate and titanium octylate were used in combination with distearylamine and laurylamine as co-catalysts (Examples 1, 2 and 4), compared with the case where tin octylate and laurylamine in Comparative Example 1 were used in combination, The same skinning time was secured. On the other hand, when iron octylate was used as the component (B) and laurylamine was used as the co-catalyst (Example 3), the skinning time was 9 hours or more, but it was confirmed that the skin was sufficiently cured after 1 day. confirmed. In addition, in any case using these carboxylic acid metal salts (Examples 1 to 4), the obtained cured product was higher in fracture than Comparative Example 1 using tin octylate and laurylamine. It exhibited strength and elongation at break. Regarding the resilience, although the restoration ratios when titanium octylate and iron octylate were used were lower than those in Comparative Example 1, both had resilience. In particular, when vanadium naphthenate was used (Example 2), high resilience was exhibited. (Example 5, Comparative Example 2) MS polymer S was used as the polyether polymer having reactive silicon as the component (A).
203 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) 95 parts by weight,
55 parts by weight of plasticizer (trade name PPG-3000), anti-sagging agent (manufactured by Kusumoto Kasei Co., Ltd., trade name DISPARON # 650)
0) 2 parts by weight, benzotriazole-based ultraviolet absorber (manufactured by Ciba-Geigy Co., Ltd., trade name Tinuvin 327) 1 part by weight, hindered amine-based light stabilizer (manufactured by Sankyo Co., Ltd., trade name Sanol LS-770) 1 part by weight The parts were weighed and mixed by hand. This was previously dried with a 5L planetary mixer at 120 ° C. for 2 hours under reduced pressure with agitation calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., trade name Shiro Gloss CC
R) 120 parts by weight, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name TYPEK R-820) 20 parts by weight and mixed to obtain 10 parts by weight.
Stir and mix for minutes. The mixture was taken out, kneaded once with three paint rolls, and then again dehydrated by reduced pressure stirring at 120 ° C. for 2 hours with a 5 L planetary mixer,
It was confirmed that the water content decreased to about 700 ppm. After cooling the mixture, dehydrating agent (Nippon Unicar Co., Ltd.)
(Manufactured by trade name A-171) 2 parts by weight was added and mixed with stirring for 15 minutes. Next, add 3 parts by weight of an aminosilane coupling agent (manufactured by Nippon Unicar Co., Ltd., trade name A-1120),
Stir-mix for 15 minutes. In addition, zirconium octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name Nikka Octix Zr: 12% toluene solution) which is the (B) component, and laurylamine (Wako Pure Co., Ltd.) which is the (C) component are further adjusted in advance. Yakuhin (manufactured by Yakuhin Co., Ltd.) was mixed in a weight ratio shown in Table 2 and mixed under reduced pressure with stirring for 5 minutes. The obtained mixture was filled in a paper cartridge (manufactured by Showa Marutsu Co., Ltd.) coated with aluminum for 1 part so as not to entrap bubbles, to obtain a 1 part type curable composition. Comparative Example 2 was prepared using 2 parts by weight of dibutyltin diacetylacetonate (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.) instead of the mixture of zirconium octylate and laurylamine.

The above one-pack type curable composition was applied at room temperature for 24 hours.
After standing for at least the time, a test body used for the tensile test was prepared as follows. A one-pack type curable composition is prepared from a one-pack type cartridge using a commercially available gun according to JIS A5758-199.
According to the method for producing the tensile adhesion test body specified in 2, an aluminum base material was assembled in an H-shape and filled. Curing condition is 2
It was set to 3 ° C. × 14 days + 50 ° C. × 14 days. In addition, the aluminum used as the base material is 50 in conformity with JIS H4000.
Alumite-treated aluminum having dimensions of x50x5 mm was used and cleaned with methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) before filling the composition. The H-type sample obtained by the above method is in a thermostatic chamber at 23 ° C. and a humidity of 50 ± 5% according to the tensile adhesion test method specified in JIS A5758-1992.
The test was performed under the conditions of a pulling speed of 50 mm / min. The stress when the cured product was stretched by 50%, 100% and 150% was M50, M100 and M150, respectively, the stress at break was TB and the elongation at break was EB.

Since the adhesiveness is an important property for the one-pack type curable composition, the adhesiveness was confirmed using anodized aluminum and vinyl chloride steel sheet. On each base material whose surface was cleaned with methyl ethyl ketone, a one-pack type curable composition was prepared from a one-pack cartridge using a commercially available gun with a width of 1 cm and a length of 3 c.
Placed in a m-shaped mountain, 23 ℃ × 14 days + 50 ℃ × 14
I was cured for a day. After curing, a hand peeling test was performed while cutting the bonded surface with a cutter knife, and the surface of the substrate was observed.
Note that CF in Table 2 means that the filled cured product shows cohesive failure, which is a failure state required for the sealing material.

The deep-part curability was obtained by filling a polyethylene tube having an inner diameter of 16.5 mm and a length of 80 mm with the one-pack type curable composition prepared in Example 5, and measuring the number of days when the tube was measured. The cured portion of the surface layer formed at the tip was taken out, and the cured thickness was measured with a caliper.

Further, in order to confirm the practicality as a one-pack type curable composition, the composition was filled in a one-pack cartridge and stored for 2 weeks in a hot air dryer whose temperature was adjusted to 50 ° C. The subsequent deep hardenability was investigated.

The results are shown in Table 2.

[0145]

[Table 2] In Example 5, with respect to the polyether polymer as the component (A) of the present invention, a zirconium carboxylic acid salt acting as a silanol condensation catalyst as the component (B), and as a co-catalyst as the component (C). By using laurylamine, the curability is slightly inferior to Comparative Example 2 using dibutyltin diacetylacetonate as a tetravalent tin catalyst, but the elongation is almost the same.
It was confirmed that a one-pack type curable composition exhibiting adhesiveness and sufficient for practical use was obtained (Table 2). (Synthesis Example 1) Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene triol having a molecular weight of about 3,000 as an initiator to give a number average molecular weight of about 26,000 (as a liquid delivery system, Tosoh HLC -8120 GPC was used, the column was Tosoh TSK-GEL H type, and the solvent was polystyrene. Then, 1.2 times the equivalent of NaO with respect to the hydroxyl groups of the hydroxyl group-terminated polypropylene oxide.
A methanol solution of Me was added to distill off the methanol,
Further, allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As described above, a trifunctional polypropylene oxide having an allyl group at the end and a number average molecular weight of about 26,000 was obtained.

In an 1 L autoclave, 500 g of the allyl-terminated trifunctional polypropylene oxide obtained above and 1 hexane
0 g was added and azeotropic dehydration was performed at 90 ° C., hexane was distilled off under reduced pressure, and then the atmosphere was replaced with nitrogen. To this, 30 μl of platinum divinyldisiloxane complex (3 wt% xylene solution in terms of platinum) was added, and then dimethoxymethylsilane 7.
0 g was added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxyalkylene polymer (A-1). The number average molecular weight of the obtained polymer (A-1) was about 26,000. In addition, ¹ H-NMR
(Using JNM-LA400 manufactured by JEOL, CDCl ₃
The silyl group introduction rate was measured by the following method (measured in a solvent). An allyl-terminated proton (CH ₂ ═CH—CH ₂ —: relative to the peak integrated value of the CH ₃ group (near 1.2 ppm) of the polypropylene oxide main chain of the allyl-terminated trifunctional polypropylene oxide before the hydrosilylation reaction.
Relative to the peak integrated value of (about 5.1 ppm): and the peak integrated value of the CH ₃ group (about 1.2 ppm) of the polypropylene oxide main chain of the silyl-terminated polypropylene oxide (A-1) after the hydrosilylation reaction, Proton of methylene group bonded to silicon atom of terminal silyl group (CH ₃ (CH ₃ O) ₂ Si—CH ₂ —CH ₂ —: 0.6 p
From the relative value of the peak integrated value (near pm): the silyl group introduction ratio (/) was 78%. (Synthesis Example 2) A 2 L pressure-resistant glass container was fitted with a three-way cock, the interior of the container was replaced with nitrogen, and then ethyl cyclohexane (with molecular sieves 3A) was left in the container for 1 night or more to dry. 262.5 ml of toluene, 787.5 ml of toluene (dried by leaving it with the molecular sieves 3A for one night or more), and 4.85 g (21.0 mmol) of p-DCC (the following compound (A)).

[0147]

[Chemical 11] Next, 438 ml of isobutylene monomer (5.15 mo
The pressure-resistant glass liquefied gas sampling tube with a needle valve containing l) was connected to a three-way cock, and the polymerization container was set to -70.
After cooling by placing in a dry ice / ethanol bath at ℃, the pressure inside the container was reduced using a vacuum pump. After opening the needle valve and introducing the isobutylene monomer from the liquefied gas sampling tube into the polymerization vessel, nitrogen was introduced from one side of the three-way cock to return the vessel to normal pressure. Next, 0.72 g (7.7 mmol) of 2-methylpyridine
Was added. Next, 10.58 ml of titanium tetrachloride (96.
5 mmol) was added to initiate polymerization. 7 from the start of polymerization
After 0 minutes, 7.20 g of allyltrimethylsilane (63.
0 mmol) was added to carry out the reaction of introducing an allyl group at the end of the molecular chain. 12 after adding allyltrimethylsilane
After 0 minutes, the reaction solution was washed with 200 ml of water four times, and the solvent was distilled off to obtain an allyl-terminated isobutylene polymer.

Next, 200 g of the allyl-terminated isobutylene polymer thus obtained was mixed with 100 g of a paraffin-based process oil (trade name Diana Process PS-32 manufactured by Idemitsu Kosan Co., Ltd.), which is a hydrocarbon plasticizer, After heating to about 75 ° C., methyldimethoxysilane was added in an amount of 2.4 equivalents to the terminal allyl group, and platinum (vinylsiloxane) complex was added in an amount of 7.5 × 10 ⁻⁵ equivalents to the terminal allyl group, and hydrosilyl was added. The chemical reaction was carried out. FT-IR
(Shimadzu IR-408) to follow the reaction,
The absorption based on the olefin at 1640 cm ^-1 disappeared in about 20 hours.

An isobutylene polymer having a reactive silicon group at both ends of a target molecular chain and PS- which is a plasticizer
A 2/1 weight ratio mixture of 32 (A-2) was obtained.

The polymer thus obtained was measured by the GPC method (LC Module 1 manufactured by Waters as a liquid feeding system, Shodex K-804 was used as a column, and CHCl ₃ was used as a solvent) to give a number average molecular weight of 17, 600, Mw / Mn (ratio of weight average molecular weight and number average molecular weight) was 1.23. In addition, ¹ H-NMR
(Using Varian Gemini 300, CDCl
Protons belonging to each structure (measured in ₃ ) (protons derived from the initiator: 6.5 to 7.5 ppm, methyl protons bonded to a silicon atom derived from the polymer end: 0.0 to
0.1 ppm and methoxy proton: 3.4 to 3.5)
As a result of measuring and comparing the intensity of the resonance signal of 1., the terminal silyl functional group number Fn (the number of silyl groups per molecule of isobutylene polymer) was 1.76. (Examples 6 to 15, Comparative Example 3) As the component (A), the reactive silicon group-containing polyoxyalkylene polymer (A-1) obtained in Synthesis Example 1 was used, and according to the formulation shown in Table 2. The various additives were weighed and kneaded well with a triple paint roll to prepare the main agent.

Next, various carboxylic acid metal salts shown in Table 1 as the component (B), which is a silanol condensation catalyst, and laurylamine as the component (C) were weighed in the above-mentioned main component, and a spatula was used. Stir and mix for 3 minutes. here,
Regarding the number of parts of the various carboxylic acid metal salts of the component (B) added, the number of moles of metal atoms contained was all the same.
After mixing, the mold having a thickness of about 3 mm was filled with a spatula and cured at 23 ° C. × 3 days + 50 ° C. × 4 days. From the obtained cured sheet, a No. 3 type dumbbell test piece specified in JIS K 6301 was punched out, and a tensile test was carried out with an autograph (pulling speed 200 mm / mi.
n). The modulus at the time of 50% elongation (M50), the strength at dumbbell rupture (Tb), and the elongation at dumbbell rupture (Eb) were measured.

Table 3 shows the blended composition of the main agent, the curing catalyst and the like, and the physical property evaluation results of the cured product obtained therefrom.

[0153]

[Table 3] As shown in Table 3, as compared with Comparative Example 3 using tin 2-ethylhexanoate as the silanol condensation catalyst, Examples 6 to
When various carboxylic acid metal salts of 15 were used, the values of Tb (breaking strength) and Eb (breaking elongation) of the physical properties of the cured product were larger, indicating high elongation and high strength. (Examples 16 to 28, Comparative Example 4) As the component (A), a mixture (A-2) of the isobutylene-based polymer having a reactive silicon group obtained in Synthesis Example 2 and a plasticizer was used. In accordance with the formulation shown, various additives were weighed and kneaded well with a triple paint roll to prepare the main agent.

Next, various carboxylic acid metal salts shown in Table 4 as the component (B), which is a silanol condensation catalyst, were weighed into the above-mentioned main component, and further, in Examples 16 to 28 and Comparative Example 4, (C).
Laurylamine was also used as a component, and the mixture was stirred and mixed for 3 minutes using a spatula. After mixing, cure at 23 ℃,
The cured state of the surface was evaluated after 5 days. Here, the addition number of the various carboxylic acid metal salts of the component (B) was such that the number of moles of the contained metal atoms was all the same.

Table 4 shows the composition of the main agent, the curing catalyst, etc., and the evaluation results of the cured state after 5 days. In addition, ○ in the table
Indicates that the surface was cured after 5 days, and x indicates that the surface was uncured after 5 days.

[0156]

[Table 4] As shown in Table 4, in the case of using the various carboxylic acid metal salts of Examples 16 to 28, the surface was cured after 5 days even though the non-tin silanol condensation catalyst was used. Showed practical curability. On the other hand, when the zinc carboxylate of Comparative Example 4 was used, the curability was poor and it was uncured after 5 days.

As described above, (A) an organic polymer having at least one reactive silicon group in the molecule, (B) calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate. , A barium carboxylate, a manganese carboxylate, a nickel carboxylate, a cobalt carboxylate, and a zirconium carboxylate, the curable composition comprising one or more carboxylic acid metal salts is a non-tin catalyst. Shows practical curability and good physical properties of cured products (high elongation and high strength)
It can be seen that it is. (Composition Using Trimethoxysilyl Group as Reactive Silicon Group) When a polyoxyalkylene-based polymer having a trimethoxysilyl group as a reactive silicon group at the terminal of the molecular chain is used, the composition is harder than the polymer of Synthesis Example 1. The speed increases. This is because the trimethoxysilyl group is more reactive than the methyldimethoxysilyl group. Such polymers are disclosed in JP-A-11-12480 and JP-A-2001-7.
2855. For example, JP-A-11
A curable composition similar to that in Examples 6 to 15 can be prepared using the polymer described in Production Example 1 of JP-1248048. The tack free time of this composition is shown in Examples 6-1.
Shorter than 5. Further, using the polymers described in Production Example 1-4 of JP 2001-72855 A, Examples 6 to
A curable composition similar to 15 can be prepared. The tack free time of this composition is shorter than Examples 6-15. Therefore, if the curing time is the same, the amount of catalyst can be reduced by using the above-mentioned polymer having a trimethoxysilyl group.

Further, when a mixture of a polymer having a trimethoxysilyl group and a polymer having a methyldimethoxysilyl group is used as the polymer, the curing time and the physical properties of the cured product can be freely controlled. For example, the curable compositions of Examples 6 to 15 were prepared using a polymer obtained by mixing a polymer having a trimethoxysilyl group and a polymer having a methyldimethoxysilyl group in a weight ratio of 1:10 to 10: 1. Can be prepared.

Examples using a polymer having a trimethoxysilyl group are shown below. (Synthesis Example 3) Polyoxy with a number average molecular weight of 17,000 and a molecular weight distribution of Mw / Mn = 1.20, which was synthesized using polypropylene oxide obtained by polymerization with a complex metal complex catalyst in a 1 L autoclave under N ₂ atmosphere. Γ-isocyanatopropyltrimethoxysilane (Y-5187 manufactured by Nippon Unicar Co., Ltd.) 19 in 1000 g of propylene diol
g and 0.05 g of dibutyltin bisisooctyl thioglycolate (U-360 manufactured by Nitto Kasei) as a catalyst were added, and this was reacted at 90 ° C. under a nitrogen stream until isocyanate groups were not detected by IR, A reactive silicon group-containing polyoxypropylene (A-3) having a trimethoxysilyl group introduced into about 80% of the above was obtained. (Examples 29 to 32) As the component (A), the polyoxyalkylene polymer (A-1) having a methyldimethoxysilyl group obtained in Synthesis Example 1 and the trimethoxysilyl group obtained in Synthesis Example 3 Using a polyoxyalkylene polymer (A-3) having
Various carboxylic acid metal salts as the component (B) and laurylamine as the component (C) were weighed and stirred for 30 seconds using a spatula and mixed. Here, the addition number of the various carboxylic acid metal salts of the component (B) was such that the number of moles of the contained metal atoms was substantially the same. After mixing, the surface was lightly pressed with a spatula, and the time until the composition did not adhere to the tip of the spatula (skinning time) was measured.

Table 5 shows the evaluation results.

[0161]

[Table 5] As shown in Table 5, a polyoxyalkylene polymer having a trimethoxysilyl group (A-3: Examples 30, 3)
2) had a faster curing rate than the polyoxyalkylene polymer having a methyldimethoxysilyl group (A-1: Examples 29 and 31).

In addition, the polyoxyalkylene polymer having a trimethoxysilyl group (A-
3) can be used to prepare curable compositions similar to those in Examples 6 to 15. The tack free time of this composition is short, and good physical properties can be obtained. (Composition Using Epoxy Resin) A curable composition similar to Examples 6 to 15 can be prepared by using a composition using a reactive silicon group-containing organic polymer and an epoxy resin. When this composition is used, the adhesive strength is rapidly developed.

[0163]

EFFECTS OF THE INVENTION (A) An organic polymer having a silicon-bonded hydroxyl group or a hydrolyzable group and having at least one silicon-containing group capable of being crosslinked by forming a siloxane bond, (B) a carboxylic acid. One or more metal carboxylate salts selected from calcium, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate and zirconium carboxylate. The curable composition characterized by containing, while exhibiting practical curability, restoration, the resulting cured product is compared to the case where tin carboxylate conventionally used as a curing catalyst is used. And has excellent mechanical properties with high strength and high elongation. Therefore, the curable composition of the present invention is extremely useful as various elastomers such as sealing materials, adhesives and pressure-sensitive adhesives.

Continued front page    (72) Inventor Katsura Wakabayashi             Hyogo Prefecture Kobe City Chuo-ku Ninomiyacho 3-1-5             504 (72) Inventor Hiroshi Ando             3-2-718 Chaenbacho, Akashi City, Hyogo Prefecture F-term (reference) 4J002 AA051 AC111 BB201 BG041                       CF001 CG001 CH051 CL001                       CN011 EG006 EN007 FD146                       FD157 GJ01 GJ02

Claims (12)

[Claims] 1. An organic polymer (A) having at least one silicon-containing group (A) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond. Contains at least one metal carboxylate selected from calcium, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate and zirconium carboxylate A curable composition comprising: 2. The curable composition according to claim 1, wherein an amine compound is an essential component as the component (C). 3. The organic polymer as the component (A) has a number average molecular weight in the range of 500 to 50,000 and has a compound represented by the general formula (1): at the terminal and / or side chain of the main chain. ] (In the formula, R ¹ and R ² each independently have 1 to 1 carbon atoms.
20 alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms (R ') ₃ SiO-
(R's are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), which is a triorganosiloxy group. Further, X is independently a hydroxyl group or a hydrolyzable group. Furthermore, a is 0, 1,
It is either 2, 3, b is 0, 1, 2, and a and b are never 0 at the same time. Also, m
Is 0 or an integer of 1 to 19), and one or more hydrolyzable silyl groups per molecule are contained in the curable composition according to claim 1 or 2. 4. The curable composition according to claim 3, wherein X is an alkoxy group. 5. The curable composition according to claim 1, wherein the organic polymer as the component (A) is a polyoxyalkylene polymer and / or a saturated hydrocarbon polymer. 6. The curable composition according to claim 5, wherein the saturated hydrocarbon polymer has a repeating unit derived from isobutylene in a total amount of 50% by weight or more. 7. The (B) component calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate, zirconium carboxylate , Each of the general formula (2)
The curable composition according to any one of claims 1 to 6, containing a carboxylic acid metal salt represented by (12) to (12) as a main component. Ca (OCOR) ₂ (2) V (OCOR) ₃ (3) Fe (OCOR) ₂ (4) Fe (OCOR) ₃ (5) Ti (OCOR) ₄ (6) K (OCOR) (7) Ba (OCOR) ) ₂ (8) Mn (OCOR) ₂ (9) Ni (OCOR) ₂ (10) Co (OCOR) ₂ (11) Zr (O) (OCOR) ₂ (12) (wherein R is substituted or unsubstituted) It is a hydrocarbon group and may contain a carbon-carbon double bond.) 8. The curable composition according to claim 1, wherein the component (B) carboxylic acid metal salt is a carboxylic acid metal salt having an acid group of a carboxylic acid having a melting point of 65 ° C. or lower. object. 9. The carboxylic acid metal salt of component (B) is a carboxylic acid metal salt having an acid group of a carboxylic acid containing a carbonyl group and having 2 to 17 carbon atoms. The curable composition according to claim 1. 10. The carboxylic acid metal salt of component (B) is a metal salt of a carboxylic acid group-containing compound selected from octylic acid, 2-ethylhexanoic acid, neodecanoic acid, oleic acid, and naphthenic acid. 8. The curable composition according to any one of 8 above. 11. An amount of 100 parts by weight of component (A),
0.005 in terms of metallic elements contained in component (B)
The curable composition according to any one of claims 1 to 10, which contains the component (B) in an amount of 5 parts by weight. 12. An amount of 100 parts by weight of the component (A),
0.005 in terms of metallic elements contained in component (B)
Component (B), component (C) 0.01 to 5 parts by weight
20 to 20 parts by weight are contained.
The curable composition according to any one of 1.